Novel sulfonyldiazomethanes, photoacid generations, resist compositions, and patterning process

ABSTRACT

A chemical amplification type resist composition contains as a photoacid generator a sulfonyldiazomethane compound of formula (1) wherein R is H or C 1-4  alkyl or alkoxy, G is SO 2  or CO, R 3  is C 1-10  alkyl or C 6-14  aryl, p is 1 or 2, q is 0 or 1, p+q=2, n is 0 or 1, m is 3 to 11, and k is 0 to 4. The composition is suited for microfabrication, especially by deep UV lithography because of many advantages including improved resolution and improved pattern profile after development.

[0001] This invention relates to novel sulfonyldiazomethane compounds,photoacid generators for resist compositions, resist compositionscomprising the photoacid generators, and a patterning process using thesame. The resist compositions, especially chemical amplification typeresist compositions are sensitive to such radiation as UV, deep UV,electron beams, x-rays, excimer laser beams, γ-rays, and synchrotronradiation and suitable for the microfabrication of integrated circuits.

BACKGROUND OF THE INVENTION

[0002] While a number of efforts are currently being made to achieve afiner pattern rule in the drive for higher integration and operatingspeeds in LSI devices, deep-ultraviolet lithography is thought to holdparticular promise as the next generation in microfabricationtechnology.

[0003] One technology that has attracted a good deal of attentionrecently utilizes as the deep UV light source a high-intensity KrFexcimer laser, especially an ArF excimer laser featuring a shorterwavelength. There is a desire to have a microfabrication technique offiner definition by combining exposure light of shorter wavelength witha resist material having a higher resolution.

[0004] In this regard, the recently developed, acid-catalyzed, chemicalamplification type resist materials are expected to comply with the deepUV lithography because of their many advantages including highsensitivity, resolution and dry etching resistance. The chemicalamplification type resist materials include positive working materialsthat leave the unexposed areas with the exposed areas removed andnegative working materials that leave the exposed areas with theunexposed areas removed.

[0005] In chemical amplification type, positive working, resistcompositions to be developed with alkaline developers, an alkali-solublephenol or a resin and/or compound in which carboxylic acid is partiallyor entirely protected with acid-labile protective groups (acid labilegroups) is catalytically decomposed by an acid which is generated uponexposure, to thereby generate the phenol or carboxylic acid in theexposed area which is removed by an alkaline developer. Also, in similarnegative working resist compositions, an alkali-soluble phenol or aresin and/or compound having carboxylic acid and a compound(crosslinking agent) capable of bonding or crosslinking the resin orcompound under the action of an acid are crosslinked with an acid whichis generated upon exposure whereby the exposed area is converted to beinsoluble in an alkaline developer and the unexposed area is removed bythe alkaline developer.

[0006] On use of the chemical amplification type, positive working,resist compositions, a resist film is formed by dissolving a resinhaving acid labile groups as a binder and a compound capable ofgenerating an acid upon exposure to radiation (to be referred to asphotoacid generator) in a solvent, applying the resist solution onto asubstrate by a variety of methods, and evaporating off the solventoptionally by heating. The resist film is then exposed to radiation, forexample, deep UV through a mask of a predetermined pattern. This isoptionally followed by post-exposure baking (PEB) for promotingacid-catalyzed reaction. The exposed resist film is developed with anaqueous alkaline developer for removing the exposed area of the resistfilm, obtaining a positive pattern profile. The substrate is then etchedby any desired technique. Finally the remaining resist film is removedby dissolution in a remover solution or ashing, leaving the substratehaving the desired pattern profile.

[0007] The chemical amplification type, positive working, resistcompositions adapted for KrF excimer lasers generally use a phenolicresin, for example, polyhydroxystyrene in which some or all of thehydrogen atoms of phenolic hydroxyl groups are protected with acidlabile protective groups. Iodonium salts, sulfonium salts, andbissulfonyldiazomethane compounds are typically used as the photoacidgenerator. If necessary, there are added additives, for example, adissolution inhibiting or promoting compound in the form of a carboxylicacid and/or phenol derivative having a molecular weight of up to 3,000in which some or all of the hydrogen atoms of carboxylic acid and/orphenolic hydroxyl groups are protected with acid labile groups, acarboxylic acid compound for improving dissolution characteristics, abasic compound for improving contrast, and a surfactant for improvingcoating characteristics.

[0008] Bissulfonyldiazomethanes as shown below are advantageously usedas the photoacid generator in chemical amplification type resistcompositions, especially chemical amplification type, positive working,resist compositions adapted for KrF excimer lasers because they providea high sensitivity and resolution and eliminate poor compatibility withresins and poor solubility in resist solvents as found with thesulfonium and iodonium salt photoacid generators.

[0009] Although these photoacid generators are highly lipophilic andhighly soluble in resist solvents, they have poor affinity to orsolubility in developers so that upon development and/or resist removal,the photoacid generators can be left on the substrate as insolublematter (consisting of the photoacid generator or a mixture thereof withthe resin).

[0010] For example, upon development, the resist material which has pooraffinity to or solubility in a developer deposits on developed spaces inthe exposed area or on lines in the unexposed area as foreign matter.

[0011] JP-A 3-103854 discloses bis(4-methoxyphenylsulfonyl)diazomethaneas a photoacid generator having a methoxy group introduced therein. Aslong as we confirmed, the methoxy group is not fully effective. Thephotoacid generator is often left on the substrate as insoluble matter(consisting of the photoacid generator or a mixture thereof with theresin) upon development and/or resist film removal.

[0012] If unsubstituted bis(phenylsulfonyl)diazomethane orbis(cyclohexylsulfonyl)diazomethane having alkyl groups instead of arylgroups is used in a resist material as the photoacid generator forreducing lipophilic property, resolution is deteriorated. If it is addedin large amounts, the problem of insoluble matter upon developmentand/or resist film removal remains unsolved.

[0013] Aside from the countermeasure for foreign matter, JP-A 10-90884discloses to introduce such an acid labile group as t-butoxycarbonyloxy,ethoxyethyl or tetrahydropyranyl into disulfonediazomethane for thepurpose of improving the contrast of positive resist material. Weempirically found that these compounds are unstable and ineffective foreliminating the foreign matter upon development and resist film removal.

[0014] Searching for a countermeasure to the foreign matter problem, wealready synthesized sulfonyldiazomethanes having an acyl group (e.g.,acetyl) or methanesulfonyl group introduced therein and found that theywere useful as the photoacid generator in chemical amplification typeresist composition. Since these arylsulfonyldiazomethanes having an acylgroup or methanesulfonyl group introduced therein lack stability underbasic conditions during their synthesis, the yield of diazo formation issometimes low. See JP-A 2001-055373 and JP-A 2001-106669.

[0015] It is known from JP-A 8-123032 to use two or more photoacidgenerators in a resist material. JP-A 11-72921 discloses the use of aradiation-sensitive acid generator comprising in admixture a compoundwhich generates a sulfonic acid having at least three fluorine atomsupon exposure to radiation and a compound which generates a fluorineatom-free sulfonic acid upon exposure to radiation, thereby improvingresolution without inviting nano-edge roughness and film surfaceroughening. JP-A 11-38604 describes that a resist composition comprisingan asymmetric bissulfonyldiazomethane such as a bissulfonyldiazomethanehaving an alkylsulfonyl or arylsulfonyl group or abissulfonyldiazomethane having an arylsulfonyl or alkoxy-substitutedarylsulfonyl group and a polyhydroxystyrene derivative having acidlabile groups as the polymer has a resolution at least comparable toprior art compositions, a sufficient sensitivity and significantlyimproved heat resistance. However, we empirically found that theseresist compositions are unsatisfactory in resolution and in the effectof eliminating the foreign matter on the pattern upon development. Fromthe synthetic and industrial standpoints, it is difficult to obtainbilaterally asymmetric bissulfonyldiazomethanes.

[0016] Aside from the above-discussed problem of insoluble matter upondevelopment and/or removal, there is also a problem that the patternprofile often changes when the period from exposure to post-exposurebaking (PEB) is prolonged, which is known as post-exposure delay (PED).Such changes frequently reveal as a slimming of the line width ofunexposed areas in the case of chemical amplification type positiveresist compositions using acetal and analogous acid labile groups, andas a thickening of the line width of unexposed areas in the case ofchemical amplification type positive resist compositions usingtert-butoxycarbonyl (t-BOC) and analogous acid labile groups. Since theperiod from exposure to PEB is often prolonged for the operationalreason, there is a desire to have a stable resist composition which isfree from such changes, that is, has PED stability.

[0017] The solubility of photosensitive agents or photoacid generatorswas the problem from the age when quinonediazide photosensitive agentswere used in non-chemical amplification type resist materials. Specificconsiderations include the solubility of photoacid generators in resistsolvents, the compatibility of photoacid generators with resins, thesolubility (or affinity) of photo-decomposed products after exposure andPEB and non-decomposed compound (photoacid generator) in a developer,and the solubility of the photoacid generator and photo-decomposedproducts thereof in a remover solvent upon resist removal or peeling. Ifthese factors are poor, there can occur problems including precipitationof the photoacid generator during storage, difficulty of filtration,uneven coating, striation, abnormal resist sensitivity, and foreignmatter, left-over and staining on the pattern and in spaces afterdevelopment.

[0018] The photoacid generator in resist material is required to meet afully high solubility in (or compatibility with) a resist solvent and aresin, good storage stability, non-toxicity, effective coating, awell-defined pattern profile, PED stability, and no foreign matter leftduring pattern formation after development and upon resist removal. Theconventional photoacid generators, especially diazodisulfone photoacidgenerators do not meet all of these requirements.

[0019] As the pattern of integrated circuits becomes finer in thesedays, a higher resolution is, of course, required, and the problem offoreign matter after development and resist removal becomes moreserious.

SUMMARY OF THE INVENTION

[0020] An object of the invention is to provide a novelsulfonyldiazomethane for use in a resist composition, especially of thechemical amplification type, such that the resist composition minimizesthe foreign matter left after coating, development and resist removaland ensures a well-defined pattern profile after development. Anotherobject of the invention is to provide a photoacid generator for resistcompositions, a resist composition comprising the photoacid generator,and a patterning process using the same.

[0021] We have found that by using a sulfonyldiazomethane compound ofthe general formula (1), especially formula (1a), to be defined below,as the photoacid generator in a resist composition, there are achieved anumber of advantages including dissolution, storage stability, effectivecoating, minimized line width variation or shape degradation duringlong-term PED, minimized foreign matter left after coating, developmentand resist removal, a well-defined pattern profile after development,and a high resolution enough for microfabrication, especially by deep UVlithography. Better results are obtained when a sulfonyldiazomethanecompound of the formula (1), especially formula (1a), is used as thephotoacid generator in a chemical amplification type resist composition,typically chemical amplification positive type resist compositioncomprising a resin which changes its solubility in an alkaline developerunder the action of an acid as a result of scission of C—O—C linkages.The composition exerts its effect to the maximum extent when processedby deep UV lithography.

[0022] In a first aspect, the invention provides a sulfonyldiazomethanecompound having the following general formula (1).

[0023] Herein R is independently hydrogen or a substituted orunsubstituted, straight, branched or cyclic alkyl or alkoxy group of 1to 4 carbon atoms, G is SO₂ or CO, R³ is a substituted or unsubstituted,straight, branched or cyclic alkyl group of 1 to 10 carbon atoms or asubstituted or unsubstituted aryl group of 6 to 14 carbon atoms, p is 1or 2, q is 0 or 1, satisfying p+q=2, n is 0 or 1, m is an integer of 3to 11, and k is an integer of 0 to 4.

[0024] Typical sulfonyldiazomethane compounds have the following generalformula (1a).

[0025] Herein R, n, m and k are as defined above.

[0026] In a second aspect, the invention provides a photoacid generatorfor a chemical amplification type resist composition comprising thesulfonyldiazomethane compound of formula (1) or (1a).

[0027] In a third aspect, the invention provides a chemicalamplification type resist composition comprising (A) a resin whichchanges its solubility in an alkaline developer under the action of anacid, (B) the sulfonyldiazomethane compound of formula (1) or (1a) whichgenerates an acid upon exposure to radiation, and optionally, (C) acompound capable of generating an acid upon exposure to radiation, otherthan component (B). The resist composition may further contain (D) abasic compound, (E) an organic acid derivative, and an organic solvent.

[0028] The resin (A) typically has such substituent groups having C—O—Clinkages that the solubility in an-alkaline developer changes as aresult of scission of the C—O—C linkages under the action of an acid.

[0029] In a preferred embodiment, the resin (A) is a polymer containingphenolic hydroxyl groups in which hydrogen atoms of the phenolichydroxyl groups are substituted with acid labile groups of one or moretypes in a proportion of more than 0 mol % to 80 mol % on the average ofthe entire hydrogen atoms of the phenolic hydroxyl groups, the polymerhaving a weight average molecular weight of 3,000 to 100,000.

[0030] More preferably, the resin (A) is a polymer comprising recurringunits of the following general formula (2a):

[0031] wherein R⁴ is hydrogen or methyl, R⁵ is a straight, branched orcyclic alkyl group of 1 to 8 carbon atoms, x is 0 or a positive integer,y is a positive integer, satisfying x+y≦5, R⁶ is an acid labile group, Sand T are positive integers, satisfying 0<T/(S+T)≦0.8,

[0032] wherein the polymer contains units in which hydrogen atoms ofphenolic hydroxyl groups are partially substituted with acid labilegroups of one or more types, a proportion of the acid labilegroup-bearing units is on the average from more than 0 mol % to 80 mol %based on the entire polymer, and the polymer has a weight averagemolecular weight of 3,000 to 100,000.

[0033] In another preferred embodiment, the resin (A) is a polymercomprising recurring units of the following general formula (2a′):

[0034] wherein R⁴ is hydrogen or methyl, R⁵ is a straight, branched orcyclic alkyl group of 1 to 8 carbon atoms, R⁶ is an acid labile group,R^(6a) is hydrogen or an acid labile group, at least some of R^(6a)being acid labile groups, x is 0 or a positive integer, y is a positiveinteger, satisfying x+y≦5, M and N are positive integers, L is 0 or apositive integer, satisfying 0<N/(M+N+L)≦0.5 and 0<(N+L)/(M+N+L)≦0.8,

[0035] wherein the polymer contains on the average from more than 0 mol% to 50 mol % of those units based on acrylate and methacrylate, andalso contains on the average from more than 0 mol % to 80 mol % of acidlabile group-bearing units, based on the entire polymer, and the polymerhas a weight average molecular weight of 3,000 to 100,000.

[0036] In a further preferred embodiment, the resin (A) is a polymercomprising recurring units of the following general formula (2a″):

[0037] wherein R⁴ is hydrogen or methyl, R⁵ is a straight, branched orcyclic alkyl group of 1 to 8 carbon atoms, R⁶ is an acid labile group,R^(6a) is hydrogen or an acid labile group, at least some of R^(6a)being acid labile groups, x is 0 or a positive integer, y is a positiveinteger, satisfying x+y≦5, yy is 0 or a positive integer, satisfyingx+yy≦5, A and B are positive integers, C, D and E each are 0 or apositive integer, satisfying 0<(B+E)/(A+B+C+D+E)≦0.5 and0<(C+D+E)/(A+B+C+D+E)≦0.8,

[0038] wherein the polymer contains on the average from more than 0 mol% to 50 mol % of those units based on indene and/or substituted indene,and also contains on the average from more than 0 mol % to 80 mol % ofacid labile group-bearing units, based on the entire polymer, and thepolymer has a weight average molecular weight of 3,000 to 100,000.

[0039] In these preferred embodiments, the acid labile group ispreferably selected from among groups of the following general formulae(4) to (7), tertiary alkyl groups of 4 to 20 carbon atoms, trialkylsilylgroups whose alkyl moieties each have 1 to 6 carbon atoms, oxoalkylgroups of 4 to 20 carbon atoms, and aryl-substituted alkyl groups of 7to 20 carbon atoms,

[0040] wherein R¹⁰ and R¹¹ each are hydrogen or a straight, branched orcyclic alkyl having 1 to 18 carbon atoms, and R¹² is a monovalenthydrocarbon group of 1 to 18 carbon atoms which may contain aheteroatom, a pair of R¹⁰ and R¹¹, R¹⁰ and R¹², or R¹¹ and R¹² maytogether form a ring, with the proviso that R¹⁰, R¹¹, and R¹² each are astraight or branched alkylene of 1 to 18 carbon atoms when they form aring,

[0041] R¹³ is a tertiary alkyl group of 4 to 20 carbon atoms, atrialkysilyl group in which each of the alkyls has 1 to 6 carbon atoms,an oxoalkyl group of 4 to 20 carbon atoms, or a group of the formula(4), z is an integer of 0 to 6,

[0042] R¹⁴ is a straight, branched or cyclic alkyl group of 1 to 8carbon atoms or an aryl group of 6 to 20 carbon atoms which may besubstituted, h is 0 or 1, i is 0, 1, 2 or 3, satisfying 2h+i=2 or 3,

[0043] R¹⁵ is a straight, branched or cyclic alkyl group of 1 to 8carbon atoms or an aryl group of 6 to 20 carbon atoms which may besubstituted, R¹⁶ to R²⁵ are each independently hydrogen or a monovalenthydrocarbon group of 1 to 15 carbon atoms which may contain aheteroatom, R¹⁶ to R²⁵, taken together, may form a ring, each of R¹⁶ toR²⁵ is a divalent hydrocarbon group of 1 to 15 carbon atoms which maycontain a heteroatom when they form a ring, or two of R¹⁶ to R²⁵ whichare attached to adjoining carbon atoms may bond together directly toform a double bond.

[0044] Preferably, the organic solvent contains a propylene glycol alkylether acetate, an alkyl lactate or a mixture thereof.

[0045] Also contemplated herein is a process for forming a pattern,comprising the steps of applying the resist composition onto a substrateto form a coating; heat treating the coating and exposing the coating tohigh energy radiation with a wavelength of up to 300 nm or electron beamthrough a photomask; optionally heat treating the exposed coating, anddeveloping the coating with a developer.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0046] Sulfonyldiazomethane

[0047] In the first aspect of the invention, novel sulfonyldiazomethanecompounds having a long-chain alkyl group or alkoxyl group are provided.They are represented by the general formula (1).

[0048] Herein R is independently hydrogen or a substituted orunsubstituted, straight, branched or cyclic alkyl or alkoxy group of 1to 4 carbon atoms, G is SO₂ or CO, and R³ is a substituted orunsubstituted, straight, branched or cyclic alkyl group of 1 to 10carbon atoms or a substituted or unsubstituted aryl group of 6 to 14carbon atoms. The subscript p is 1 or 2, q is 0 or 1, satisfying p+q=2,n is 0 or 1, m is an integer of 3 to 11, and k is an integer of 0 to 4.

[0049] Preferred among the sulfonyldiazomethane compounds of formula (1)are sulfonyldiazomethane compounds having long-chain alkyl or alkoxylgroups of the following general formula (1a).

[0050] Herein R is independently hydrogen or a substituted orunsubstituted, straight, branched or cyclic alkyl or alkoxy group of 1to 4 carbon atoms, n is 0 or 1, m is an integer of 3 to 11, and k is aninteger of 0 to 4.

[0051] In formula (1) or (1a), R may be the same or different and standsfor hydrogen or substituted or unsubstituted, straight, branched orcyclic alkyl or alkoxy groups of 1 to 4 carbon atoms, for example,hydrogen, methyl, ethyl, n-propyl, sec-propyl, cyclopropyl, n-butyl,sec-butyl, iso-butyl, tert-butyl, methoxy, ethoxy, n-propyloxy,sec-propyloxy, n-butyloxy, sec-butyloxy, iso-butyloxy, andtert-butyloxy. Of these, hydrogen, methyl, ethyl, n-propyl and isopropylare preferred, with hydrogen and methyl being most preferred.

[0052] The subscript k is an integer of 0 to 4, and k is preferably 0, 1or 2 when R is C₁₋₄ alkyl or alkoxy. The substitution position of R isarbitrary and preferably 2-position (ortho position) relative to thesulfonyl group. It is more preferred that methyl be located at the2-position (ortho position) relative to the sulfonyl group. When k is 2to 4, substituent groups (R) which may be either identical or differentmay be further located at positions other than 2-position.

[0053] In formula (1) or (1a), R³ stands for substituted orunsubstituted, straight, branched or cyclic alkyl groups of 1 to 10carbon atoms or substituted or unsubstituted aryl groups of 6 to 14carbon atoms. Illustrative, non-limiting, examples of the straight,branched or cyclic alkyl groups include methyl, ethyl, n-propyl,sec-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl,sec-pentyl, cyclopentyl, n-hexyl, and cyclohexyl. Illustrative,non-limiting, examples of the substituted or unsubstituted aryl groupsinclude phenyl, 4-methylphenyl, 4-ethylphenyl, 4-methoxyphenyl,4-tert-butylphenyl, 4-tert-butoxyphenyl, 4-cyclohexylphenyl,4-cyclohexyloxyphenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl,2,4,6-triisopropylphenyl, 1-naphthyl and 2-naphthyl. Of these,tert-butyl, cyclohexyl, 4-methylphenyl, 2,4-dimethylphenyl and4-tert-butylphenyl are preferred. G stands for SO₂ or CO. SO₂ ispreferred.

[0054] The subscript p is equal to 1 or 2, q is equal to 0 or 1,satisfying p+q=2.

[0055] The subscript n is equal to 0 or 1. Preference is given to n=1for ease of availability of starting reactants and ease of synthesis. Inthe case of n=0, a maximum absorption peak near 255 nm attributable toalkoxyphenyl group can be shifted so that the transmittance at 248 nm isincreased as compared with the case where n=1. In this sense, n isselected equal to 0 or 1 depending on the desired transmittance ofresist. The subscript m is an integer of 3 to 11, preferably 5 to 9.Where m is less than 3, the problem of foreign matter left upondevelopment and resist film peeling is not overcome. A value of m inexcess of 11 raises problems of synthesis including too high a boilingpoint of starting thiol reactant.

[0056] The sulfonyldiazomethane compounds can be synthesized by thefollowing method although the synthesis method is not limited thereto.

[0057] Reference is first made to a sulfonyldiazomethane compound offormula (1) wherein p=2, that is, a symmetric bissulfonyldiazomethanecompound. It is desirably synthesized by condensing a substitutedthiophenol with dichloromethane under basic conditions as disclosed inJP-A 3-103854. More specifically, an alkyl or alkoxyl-containingthiophenol such as 4-(n-hexyloxy)thiophenol is condensed withdichloromethane in an alcohol solvent such as methanol or ethanol in thepresence of a base such as sodium hydroxide or potassium hydroxide,obtaining a formaldehyde bis(alkylphenylthio)acetal or formaldehydebis(alkoxyphenylthio)acetal.

[0058] Herein, R, n, m and k are as defined above.

[0059] Alternatively, a substituted thiophenol is condensed withformaldehyde (para-formaldehyde) under acidic conditions such assulfuric acid or trifluoromethanesulfonic acid.

[0060] In the case of p=1, that is, an asymmetric sulfonyldiazomethanecompound, reaction is effected between a halomethylthio ether and analkyl or alkoxy-substituted thiophenol. In the case ofsulfonylcarbonyldiazomethane, reaction is conducted between anα-halomethylketone and an alkyl or alkoxy-substituted thiophenol. Thehalomethylthio ether can be prepared from a corresponding thiol,formaldehyde and hydrogen chloride (see J. Am. Chem. Soc., 86, 4383(1964), J. Am. Chem. Soc., 67, 655 (1945), and U.S. Pat. No. 2,354,229).

[0061] Herein, R, R³, n, m and k are as defined above, and X is ahalogen atom.

[0062] In the above procedures, an alkyl or alkoxy-substitutedthiophenol is used as the starting reactant. In the case of n=1, thatis, having an alkoxyl group, a possible method is by using ahydroxythiophenol as the starting reactant and reacting it with acorresponding alkyl halide as shown below.

[0063] Herein, R, R³, n, m and k are as defined above, and X is ahalogen atom.

[0064] Further, the product is oxidized with an oxidant such as aqueoushydrogen peroxide in the presence of sodium tungstate etc. as describedin JP-A 4-211258, yielding a corresponding sulfonylmethane.

[0065] Herein, R, R³, n, m and k are as defined above.

[0066] This product is reacted with p-toluenesulfonylazide,p-dodecylbenzenesulfonylazide or p-acetamidobenzenesulfonylazide underbasic conditions into a diazo form, yielding the endsulfonyldiazomethane.

[0067] Herein, R, R³, p, q, n, m, k and G are as defined above.

[0068] It is noted that the synthesis of alkyl- or alkoxy-substitutedthiophenols is not critical. It can be synthesized by converting analkyl- or alkoxybenzene with chlorosulfuric acid, sulfuric acid/aceticanhydride or the like to a substituted benzene sulfonic acid, thenconverting it with chlorosulfuric acid, thionyl chloride or the like toa substituted benzene sulfonyl chloride, and reducing it with aluminumlithium hydride, hydrochloric acid/zinc or the like as shown below.

[0069] Herein R, n, m and k are as defined above.

[0070] The halogenated alkylbenzene or halogenated alkoxybenzene istreated with metallic magnesium to form a Grignard reagent, which isreacted with sulfur for acidification. See Romeo B. Wagner and Harry D.Zook, Synthetic Organic Chemistry, John Wiley & Sons, Inc., 1965,778-781.

[0071] Herein R, n, m and K are as defined above, and X is a halogenatom.

[0072] The halogenated alkoxybenzene can be synthesized by reacting ahalogenated phenol with CH₃(CH₂)_(m)X under basic conditions. Exemplaryof suitable halogenated phenols are 4-bromophenol,4-bromo-2,6-dimethylphenol, 4-chloro-2-methylphenol,4-chloro-3-methylphenol, 4-chloro-2-isopropyl-5-methylphenol, and3-ethyl-4-chlorophenol. Alternatively, it can be synthesized by reactinga phenol derivative with CH₃(CH₂)_(m)X under basic conditions, followedby reaction with bromine. Exemplary of suitable phenol derivatives arephenol, cresol, xylenol, trimethylphenol, thymol, isothymol,ethylphenol, and 2-tert-butyl-5-methylphenol.

[0073] Examples of the sulfonyldiazomethanes of formulae (1) and (1a)are illustrated below, but are not limited thereto. Examples ofbilaterally symmetric bissulfonyldiazomethane includebis(4-n-butylphenylsulfonyl)diazomethane,bis(4-n-pentylphenylsulfonyl)diazomethane,bis(4-n-hexylphenylsulfonyl)diazomethane,bis(4-n-heptylphenylsulfonyl)diazomethane,bis(4-n-octylphenylsulfonyl)diazomethane,bis(4-n-nonylphenylsulfonyl)diazomethane,bis(4-n-decylphenylsulfonyl)diazomethane,bis(4-n-undecylphenylsulfonyl)diazomethane,bis(4-n-dodecylphenylsulfonyl)diazomethane,bis(4-(n-butyloxy)phenylsulfonyl)diazomethane,bis(4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(4-(n-heptyloxy)phenylsulfonyl)diazomethane,bis(4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(4-(n-nonyloxy)phenylsulfonyl)diazomethane,bis(4-(n-decyloxy)phenylsulfonyl)diazomethane,bis(4-(n-undecyloxy)phenylsulfonyl)diazomethane,bis(4-(n-dodecyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-butyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-heptyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-nonyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-decyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-undecyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-dodecyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-butyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-heptyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-nonyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-decyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-undecyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-dodecyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-butyloxy)-phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-heptyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-nonyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-decyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-undecyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-dodecyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-butyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-heptyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-nonyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-decyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-undecyloxy)phenylsulfonyl)diazomethane,andbis(5-isopropyl-2-methyl-4-(n-dodecyloxy)phenylsulfonyl)diazomethane.

[0074] Examples of the bilaterally asymmetric sulfonyldiazomethaneinclude (4-(n-hexyloxy)phenylsulfonyl)(methylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(tert-butylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(cyclohexylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(benzenesulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(p-toluenesulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(2,4-dimethylphenylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(4-tert-butylphenylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(4-tert-butoxyphenylsulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(methylsulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(tert-butylsulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(cyclohexylsulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(benzenesulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(p-toluene-sulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(2,4-dimethylphenylsulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(4-tert-butylphenylsulfonyl)diazomethane,and(4-(n-octyloxy)phenylsulfonyl)(4-tert-butoxyphenylsulfonyl)diazomethane.

[0075] Examples of the sulfonylcarbonyldiazomethane include(4-(n-hexyloxy)phenylsulfonyl)(methylcarbonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(tert-butylcarbonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(cyclohexylcarbonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(benzoyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(p-toluenecarbonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(2,4-dimethylphenylcarbonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(4-tert-butylphenylcarbonyl)diazomethane,and(4-(n-hexyloxy)phenylsulfonyl)(4-tert-butoxyphenylcarbonyl)diazomethane.

[0076] Of these, preferred arebis(4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(2,5-dimethyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-5-isopropyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane, andthe like.

[0077] Examples of the sulfonyl diazomethane of the general formula (1a)include the compounds having the following formula.

[0078] Herein m is as defined above.

[0079] The sulfonyldiazomethane compounds of formula (1) or (1a) areuseful as the photoacid generator in resist materials sensitive toradiation such as ultraviolet, deep ultraviolet, electron beams, x-rays,excimer laser light, γ-rays, and synchrotron radiation for use in themicrofabrication of integrated circuits, especially in chemicalamplification type resist materials.

[0080] Resist Composition

[0081] The resist compositions of the invention contain one or more ofthe sulfonyldiazomethane compounds of formula (1) or (1a). The resistcompositions may be either positive or negative working although theyare preferably of the chemical amplification type. The resistcompositions of the invention include a variety of embodiments,

[0082] 1) a chemically amplified positive working resist compositioncomprising (A) a resin which changes its solubility in an alkalinedeveloper under the action of an acid, (B) a sulfonyldiazomethanecompound capable of generating an acid upon exposure to radiationrepresented by the general formula (1) or (1a), and (F) an organicsolvent;

[0083] 2) a chemically amplified positive working resist compositionof 1) further comprising (C) a photoacid generator capable of generatingan acid upon exposure to radiation other than component (B);

[0084] 3) a chemically amplified positive working resist compositionof 1) or 2) further comprising (D) a basic compound;

[0085] 4) a chemically amplified positive working resist compositionof 1) to 3) further comprising (E) an organic acid derivative;

[0086] 5) a chemically amplified positive working resist compositionof 1) to 4) further comprising (G) a compound with a molecular weight ofup to 3,000 which changes its solubility in an alkaline developer underthe action of an acid;

[0087] 6) a chemically amplified negative working resist compositioncomprising (B) a sulfonyldiazomethane compound capable of generating anacid upon exposure to radiation represented by the general formula (1)or (1a), (F) an organic solvent, (H) an alkali-soluble resin, and (I) anacid crosslinking agent capable of forming a crosslinked structure underthe action of an acid;

[0088] 7) a chemically amplified negative working resist composition of6) further comprising (C) another photoacid generator;

[0089] 8) a chemically amplified negative working resist composition of6) or 7) further comprising (D) a basic compound; and

[0090] 9) a chemically amplified negative working resist composition of6) to 8) further comprising (J) an alkali soluble compound having amolecular weight of up to 2,500; but not limited thereto.

[0091] Now the respective components are described in detail.

[0092] Component (A)

[0093] Component (A) is a resin which changes its solubility in analkaline developer solution under the action of an acid. It ispreferably, though not limited thereto, an alkali-soluble resin havingphenolic hydroxyl and/or carboxyl groups in which some or all of thephenolic hydroxyl and/or carboxyl groups are protected with acid-labileprotective groups having a C—O—C linkage.

[0094] The alkali-soluble resins having phenolic hydroxyl and/orcarboxyl groups include homopolymers and copolymers of p-hydroxystyrene,m-hydroxystyrene, α-methyl-p-hydroxystyrene, 4-hydroxy-2-methylstyrene,4-hydroxy-3-methylstyrene, hydroxyindene, methacrylic acid and acrylicacid, and such copolymers having a carboxylic derivative or diphenylethylene introduced at their terminus.

[0095] Also included are copolymers in which units free ofalkali-soluble sites such as styrene, α-methylstyrene, acrylate,methacrylate, hydrogenated hydroxystyrene, maleic anhydride, maleimide,substituted or unsubstituted indene are introduced in addition to theabove-described units in such a proportion that the solubility in analkaline developer may not be extremely reduced. Substituents on theacrylates and methacrylates may be any of the substituents which do notundergo acidolysis. Exemplary substituents are straight, branched orcyclic C₁₋₈ alkyl groups and aromatic groups such as aryl groups, butnot limited thereto.

[0096] Examples of the alkali-soluble resins or polymers are givenbelow. These polymers may also be used as the material from which theresin (A) which changes its solubility in an alkaline developer underthe action of an acid is prepared and as the alkali-soluble resin whichserves as component (H) to be described later. Examples includepoly(p-hydroxystyrene), poly(m-hydroxystyrene),poly(4-hydroxy-2-methylstyrene), poly(4-hydroxy-3-methylstyrene),poly(α-methyl-p-hydroxystyrene), partially hydrogenated p-hydroxystyrenecopolymers, p-hydroxystyrene-α-methyl-p-hydroxystyrene copolymers,p-hydroxystyrene-α-methylstyrene copolymers, p-hydroxystyrene-styrenecopolymers, p-hydroxystyrene-m-hydroxystyrene copolymers,p-hydroxystyrene-styrene copolymers, p-hydroxystyrene-indene copolymers,p-hydroxystyrene-acrylic acid copolymers, p-hydroxystyrene-methacrylicacid copolymers, p-hydroxystyrene-methyl acrylate copolymers,p-hydroxystyrene-acrylic acid-methyl methacrylate copolymers,p-hydroxystyrene-methyl methacrylate copolymers,p-hydroxystyrene-methacrylic acid-methyl methacrylate copolymers,poly(methacrylic acid), poly(acrylic acid), acrylic acid-methyl acrylatecopolymers, methacrylic acid-methyl methacrylate copolymers, acrylicacid-maleimide copolymers, methacrylic acid-maleimide copolymers,p-hydroxystyrene-acrylic acid-maleimide copolymers, andp-hydroxystyrene-methacrylic acid-maleimide copolymers, but are notlimited to these combinations.

[0097] Preferred are poly(p-hydroxystyrene), partially hydrogenatedp-hydroxystyrene copolymers, p-hydroxystyrene-styrene copolymers,p-hydroxystyrene-indene copolymers, p-hydroxystyrene-acrylic acidcopolymers, and p-hydroxystyrene-methacrylic acid copolymers.

[0098] Alkali-soluble resins comprising units of the following formula(2), (2′) or (2″) are especially preferred.

[0099] Herein R⁴ is hydrogen or methyl, R⁵ is a straight, branched orcyclic alkyl group of 1 to 8 carbon atoms, x is 0 or a positive integer,y is a positive integer, satisfying x+y≦5, M and N are positiveintegers, satisfying 0<N/(M+N)≦0.5, and A and B are positive integers,and C is 0 or a positive integer, satisfying 0<B/(A+B+C)≦0.5.

[0100] The polymer of formula (2″) can be synthesized, for example, byeffecting thermal polymerization of an acetoxystyrene monomer, atertiary alkyl (meth)acrylate monomer and an indene monomer in anorganic solvent in the presence of a radical initiator, and subjectingthe resulting polymer to alkaline hydrolysis in an organic solvent fordeblocking the acetoxy group, for thereby forming a ternary copolymer ofhydroxystyrene, tertiary alkyl (meth)acrylate and indene. The organicsolvent used during polymerization is exemplified by toluene, benzene,tetrahydrofuran, diethyl ether and dioxane. Exemplary polymerizationinitiators include 2,2′-azobisisobutyronitrile,2,2′-azobis(2,4-dimethylvaleronitrile),dimethyl-2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroylperoxide. Polymerization is preferably effected while heating at 50 to80° C. The reaction time is usually about 2 to 100 hours, preferablyabout 5 to 20 hours. Aqueous ammonia, triethylamine or the like may beused as the base for the alkaline hydrolysis. For the alkalinehydrolysis, the temperature is usually −20° C. to 100° C., preferably 0°C. to 60° C., and the time is about 0.2 to 100 hours, preferably about0.5 to 20 hours.

[0101] Also included are polymers having the dendritic or hyperbranchedpolymer structure of formula (2″′) below.

[0102] Herein ZZ is a divalent organic group selected from among CH₂,CH(OH), CR⁵(OH), C═O and C(OR⁵)(OH) or a trivalent organic grouprepresented by —C(OH)═. Subscript F, which may be identical ordifferent, is a positive integer, and H is a positive integer,satisfying 0.001≦H/(H+F)≦0.1, and XX is 1 or 2. R⁴, R⁵, x and y are asdefined above.

[0103] The dendritic or hyperbranched polymer of phenol derivative canbe synthesized by effecting living anion polymerization of apolymerizable monomer such as 4-tert-butoxystyrene and reacting abranching monomer such as chloromethylstyrene as appropriate during theliving anion polymerization.

[0104] For the detail of synthesis, reference is made to JP-A2000-344836.

[0105] The alkali-soluble resins or polymers should preferably have aweight average molecular weight (Mw) of 3,000 to 100,000. Many polymerswith Mw of less tan 3,000 do not perform well and are poor in heatresistance and film formation. Many polymers with Mw of more than100,000 give rise to a problem with respect to dissolution in the resistsolvent and developer. The polymer should also preferably have adispersity (Mw/Mn) of up to 3.5, and more preferably up to 1.5. With adispersity of more than 3.5, resolution is low in many cases. Althoughthe preparation method is not critical, a poly(p-hydroxystyrene) orsimilar polymer with a low dispersity or narrow dispersion can besynthesized by living anion polymerization.

[0106] In the resist composition using the sulfonyldiazomethane offormula (1), a resin having such substituent groups with C—O—C linkages(acid labile groups) that the solubility in an alkaline developerchanges as a result of severing of the C—O—C linkages under the actionof an acid, especially an alkali-soluble resin as mentioned above ispreferably used as component (A). Especially preferred is a polymercomprising recurring units of the above formula (2) and containingphenolic hydroxyl groups in which hydrogen atoms of the phenolichydroxyl groups are substituted with acid labile groups of one or moretypes in a proportion of more than 0 mol % to 80 mol % on the average ofthe entire hydrogen atoms of the phenolic hydroxyl group, the polymerhaving a weight average molecular weight of 3,000 to 100,000.

[0107] Also preferred is a polymer comprising recurring units of theabove formula (2′), that is, a copolymer comprising p-hydroxystyreneand/or α-methyl-p-hydroxystyrene and acrylic acid and/or methacrylicacid, wherein some of the hydrogen atoms of the carboxyl groups ofacrylic acid and/or methacrylic acid are substituted with acid labilegroups of one or more types, and the units based on acrylate and/ormethacrylate are contained in a proportion of more than 0 mol % to 50mol %, on the average, of the copolymer, and wherein some of thehydrogen atoms of the phenolic hydroxyl groups of p-hydroxystyreneand/or α-methyl-p-hydroxystyrene may be substituted with acid labilegroups of one or more types. In the preferred copolymer, the units basedon acrylate and/or methacrylate having acid labile groups substitutedthereon and optionally the units based on p-hydroxystyrene and/orα-methyl-p-hydroxystyrene having acid labile groups substituted thereonare contained in a proportion of more than 0 mol % to 80 mol %, on theaverage, of the copolymer.

[0108] Alternatively, a polymer comprising recurring units of the aboveformula (2″), that is, a copolymer comprising p-hydroxystyrene and/orα-methyl-p-hydroxystyrene and substituted and/or unsubstituted indene,is preferred wherein some of the hydrogen atoms of the phenolic hydroxylgroups of p-hydroxystyrene and/or α-methyl-p-hydroxystyrene aresubstituted with acid labile groups of one or more types, and some ofthe hydrogen atoms of the carboxyl groups of acrylic acid and/ormethacrylic acid are substituted with acid labile groups of one or moretypes. Where the substituted indene has hydroxyl groups, some of thehydrogen atoms of these hydroxyl groups may be substituted with acidlabile groups of one or more types. In the preferred copolymer, theunits based on p-hydroxystyrene and/or α-methyl-p-hydroxystyrene havingacid labile groups substituted thereon, the units based on acrylic acidand/or methacrylic acid having acid labile groups substituted thereon,and the units based on indene having acid labile groups substitutedthereon are contained in a proportion of more than 0 mol % to 80 mol %,on the average, of the copolymer.

[0109] Exemplary and preferred such polymers are polymers or highmolecular weight compounds comprising recurring units represented by thefollowing general formula (2a), (2a′) or (2a″) and having a weightaverage molecular weight of 3,000 to 100,000.

[0110] Herein, R⁴ is hydrogen or methyl. R⁵ is a straight, branched orcyclic alkyl group of 1 to 8 carbon atoms. Letter x is 0 or a positiveinteger, and y is a positive integer, satisfying x+y≦5. R⁶ is an acidlabile group. S and T are positive integers, satisfying 0<T/(S+T)≦0.8.R^(6a) is hydrogen or an acid labile group, at least some of the R^(6a)groups are acid labile groups. M and N are positive integers, L is 0 ora positive integer, satisfying 0<N/(M+N+L)≦0.5 and 0<(N+L)/(M+N+L)≦0.5.The letter yy is 0 or a positive integer, satisfying x+yy≦5. A and B arepositive integers, C, D and E each are 0 or a positive integer,satisfying 0<(B+E)/(A+B+C+D+E)≦0.5 and 0<(C+D+E)/(A+B+C+D+E)≦0.8.

[0111] R⁵ stands for straight, branched or cyclic C₁₋₈ alkyl groups, forexample, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl,tert-butyl, cyclohexyl and cyclopentyl.

[0112] With respect to the acid labile groups, where some of thephenolic hydroxyl groups and some or all of the carboxyl groups in thealkali-soluble resin are protected with acid labile groups having C—O—Clinkages, the acid labile groups are selected from a variety of suchgroups. The preferred acid labile groups are groups of the followinggeneral formulae (4) to (7), tertiary alkyl groups of 4 to 20 carbonatoms, preferably 4 to 15 carbon atoms, trialkylsilyl groups whose alkylgroups each have 1 to 6 carbon atoms, oxoalkyl groups of 4 to 20 carbonatoms, or aryl-substituted alkyl groups of 7 to 20 carbon atoms.

[0113] Herein R¹⁰ and R¹¹ are independently hydrogen or straight,branched or cyclic alkyl groups of 1 to 18 carbon atoms, preferably 1 to10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl andn-octyl. R¹² is a monovalent hydrocarbon group of 1 to 18 carbon atoms,preferably 1 to 10 carbon atoms, which may have a hetero atom (e.g.,oxygen atom), for example, straight, branched or cyclic alkyl groups,and such groups in which some hydrogen atoms are substituted withhydroxyl, alkoxy, oxo, amino or alkylamino groups. Illustrative examplesof the substituted alkyl groups are given below.

[0114] A pair of R¹⁰ and R¹¹, a pair of R¹⁰ and R¹², or a pair of R¹¹and R¹², taken together, may form a ring. Each of R¹⁰, R¹¹ and R¹² is astraight or branched alkylene group of 1 to 18 carbon atoms, preferably1 to 10 carbon atoms, when they form a ring.

[0115] R¹³ is a tertiary alkyl group of 4 to 20 carbon atoms, preferably4 to 15 carbon atoms, a trialkylsilyl group whose alkyl groups each have1 to 6 carbon atoms, an oxoalkyl group of 4 to 20 carbon atoms or agroup of formula (4). Exemplary tertiary alkyl groups are tert-butyl,tert-amyl, 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl,1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl,1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl and1-adamantyl-1-methylethyl. Exemplary trialkylsilyl groups aretrimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl. Exemplaryoxoalkyl groups are 3-oxocyclohexyl, 4-methyl-2-oxooxan-4-yl, and5-methyl-5-oxooxolan-4-yl. Letter z is an integer of 0 to 6.

[0116] R¹⁴ is a straight, branched or cyclic alkyl group of 1 to 8carbon atoms or substituted or unsubstituted aryl group of 6 to 20carbon atoms. Exemplary straight, branched or cyclic alkyl groupsinclude methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl,cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl andcyclohexylethyl. Exemplary substituted or unsubstituted aryl groupsinclude phenyl, methylphenyl, naphthyl, anthryl, phenanthryl, andpyrenyl. Letter h is equal to 0 or 1, i is equal to 0, 1, 2 or 3,satisfying 2h+i=2 or 3.

[0117] R¹⁵ is a straight, branched or cyclic alkyl group of 1 to 8carbon atoms or substituted or unsubstituted aryl group of 6 to 20carbon atoms, examples of which are as exemplified for R¹⁴. R¹⁶ to R²⁵are independently hydrogen or monovalent hydrocarbon groups of 1 to 15carbon atoms which may contain a hetero atom, for example, straight,branched or cyclic alkyl groups such as methyl, ethyl, propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl,n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, cyclopentylmethyl,cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl,and cyclohexylbutyl, and substituted ones of these groups in which somehydrogen atoms are substituted with hydroxyl, alkoxy, carboxy,alkoxycarbonyl, oxo, amino, alkylamino, cyano, mercapto, alkylthio, andsulfo groups. R¹⁶ to R²⁵, for example, a pair of R¹⁶ and R¹⁷, a pair ofR¹⁶ and R¹⁸, a pair of R¹⁷ and R¹⁹, a pair of R¹⁸ and R¹⁹, a pair of R²⁰and R²¹, or a pair of R²² and R²³, taken together, may form a ring. WhenR¹⁶ to R²⁶ form a ring, they are divalent hydrocarbon groups of 1 to 15carbon atoms which may contain a hetero atom, examples of which are theabove-exemplified monovalent hydrocarbon groups with one hydrogen atomeliminated. Also, two of R¹⁶ to R²⁵ which are attached to adjacentcarbon atoms (for example, a pair of R¹⁶ and R¹⁸, a pair of R¹⁸ and R²⁴,or a pair of R²² and R²⁴) may directly bond together to form a doublebond.

[0118] Of the acid labile groups of formula (4), illustrative examplesof the straight or branched groups are given below.

[0119] Of the acid labile groups of formula (4), illustrative examplesof the cyclic groups include tetrahydrofuran-2-yl,2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl and2-methyltetrahydropyran-2-yl.

[0120] Illustrative examples of the acid labile groups of formula (5)include tert-butoxycarbonyl, tert-butoxycarbonylmethyl,tert-amyloxycarbonyl, tert-amyloxycarbonyl-methyl,1,1-diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl,1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl,1-ethyl-2-cyclopentenyloxycarbonyl,1-ethyl-2-cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl,2-tetrahydropyranyloxycarbonylmethyl, and2-tetrahydrofuranyloxycarbonylmethyl.

[0121] Illustrative examples of the acid labile groups of formula (6)include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl,1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec-butylcyclopentyl,1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl,3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexen-3-yl,3-ethyl-1-cylclohexen-3-yl, and 1-cyclohexyl-cyclopentyl.

[0122] Illustrative examples of the acid labile groups of formula (7)are given below.

[0123] Exemplary of the tertiary alkyl group of 4 to 20 carbon atoms,preferably 4 to 15 carbon atoms, are tert-butyl, tert-amyl,3-ethyl-3-pentyl and dimethylbenzyl.

[0124] Exemplary of the trialkylsilyl groups whose alkyl groups eachhave 1 to 6 carbon atoms are trimethylsilyl, triethylsilyl, andtert-butyldimethylsilyl.

[0125] Exemplary of the oxoalkyl groups of 4 to 20 carbon atoms are3-oxocyclohexyl and groups represented by the following formulae.

[0126] Exemplary of the aryl-substituted alkyl groups of 7 to 20 carbonatoms are benzyl, methylbenzyl, dimethylbenzyl, diphenylmethyl, and1,1-diphenylethyl.

[0127] In the resist composition comprising the sulfonyldiazomethane asa photoacid generator, the resin (A) which changes its solubility in analkaline developer under the action of an acid may be the polymer offormula (2) or (2′), (2″) or (2″′) in which some of the hydrogen atomsof the phenolic hydroxyl groups are crosslinked within a molecule and/orbetween molecules, in a proportion of more than 0 mol % to 50 mol %, onthe average, of the entire phenolic hydroxyl groups on the polymer, withcrosslinking groups having C—O—C linkages represented by the followinggeneral formula (3). With respect to illustrative examples and synthesisof polymers crosslinked with acid labile groups, reference should bemade to JP-A 11-190904.

[0128] Herein, each of R⁷ and R⁸ is hydrogen or a straight, branched orcyclic alkyl group of 1 to 8 carbon atoms, or R⁷ and R⁸, taken together,may form a ring, and each of R⁷ and R⁸ is a straight or branchedalkylene group of 1 to 8 carbon atoms when they form a ring. R⁹ is astraight, branched or cyclic alkylene group of 1 to 10 carbon atoms.Letter “b” is 0 or an integer of 1 to 10. AA is an a-valent aliphatic oralicyclic saturated hydrocarbon group, aromatic hydrocarbon group orheterocyclic group of 1 to 50 carbon atoms, which may be separated by ahetero atom and in which some of the hydrogen atom attached to carbonatoms may be substituted with hydroxyl, carboxyl, carbonyl or halogen.Letter “a” is an integer of 1 to 7.

[0129] Preferably in formula (3), R⁷ is methyl, R⁸ is hydrogen, a is 1,b is 0, and AA is ethylene, 1,4-butylene or 1,4-cyclohexylene.

[0130] It is noted that these polymers which are crosslinked within themolecule or between molecules with crosslinking groups having C—O—Clinkages can be synthesized by reacting a corresponding non-crosslinkedpolymer with an alkenyl ether in the presence of an acid catalyst in aconventional manner.

[0131] If decomposition of other acid labile groups proceeds under acidcatalyst conditions, the end product can be obtained by once reactingthe alkenyl ether with hydrochloric acid or the like for conversion to ahalogenated alkyl ether and reacting it with the polymer under basicconditions in a conventional manner.

[0132] Illustrative, non-limiting, examples of the alkenyl ether includeethylene glycol divinyl ether, triethylene glycol divinyl ether,1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether,1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, neopentylglycol divinyl ether, trimethylolpropane trivinyl ether,trimethylolethane trivinyl ether, hexanediol divinyl ether, and1,4-cyclohexanediol divinyl ether.

[0133] In the chemical amplification type positive resist composition,the resin used as component (A) is as described above while thepreferred acid labile groups to be substituted for phenolic hydroxylgroups are 1-ethoxyethyl, 1-ethoxypropyl, tetrahydrofuranyl,tetrahydropyranyl, tert-butyl, tert-amyl,1-ethylcyclohexyloxycarbonylmethyl, tert-butoxycarbonyl,tert-butoxycarbonylmethyl, and substituents of formula (3) wherein R⁷ ismethyl, R⁸ is hydrogen, a is 1, b is equal to 0, and AA is ethylene,1,4-butylene or 1,4-cyclohexylene. Also preferably, the hydrogen atomsof carboxyl groups of methacrylic acid or acrylic acid are protectedwith substituent groups as typified by tert-butyl, tert-amyl,2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 1-ethylcyclopentyl,1-ethylcyclohexyl, 1-cyclohexylcyclopentyl, 1-ethylnorbornyl,tetrahydrofuranyl and tetrahydropyranyl.

[0134] In a single polymer, these substituents may be incorporated aloneor in admixture of two or more types. A blend of two or more polymershaving substituents of different types is also acceptable.

[0135] The percent proportion of these substituents substituting forphenol and carboxyl groups in the polymer is not critical. Preferablythe percent substitution is selected such that when a resist compositioncomprising the polymer is applied onto a substrate to form a coating,the unexposed area of the coating may have a dissolution rate of 0.01 to10 Å/sec in a 2.38% tetramethylammonium hydroxide (TMAH) developer.

[0136] On use of a polymer containing a greater proportion of carboxylgroups which can reduce the alkali dissolution rate, the percentsubstitution must be increased or non-acid-decomposable substituents tobe described later must be introduced.

[0137] When acid labile groups for intramolecular and/or intermolecularcrosslinking are to be introduced, the percent proportion ofcrosslinking substituents is preferably up to 20 mol %, more preferablyup to 10 mol %, based on the entire hydrogen atoms of phenolic hydroxylgroups. If the percent substitution of crosslinking substituents is toohigh, crosslinking results in a higher molecular weight which canadversely affect dissolution, stability and resolution. It is alsopreferred to further introduce another non-crosslinking acid labilegroup into the crosslinked polymer at a percent substitution of up to 10mol % for adjusting the dissolution rate to fall within the above range.

[0138] In the case of poly(p-hydroxystyrene), the optimum percentsubstitution differs between a substituent having a strong dissolutioninhibitory action such as a tert-butoxycarbonyl group and a substituenthaving a weak dissolution inhibitory action such as an acetal groupalthough the overall percent substitution is preferably 10 to 40 mol %,more preferably 20 to 30 mol %, based on the entire hydrogen atoms ofphenolic hydroxyl groups in the polymer.

[0139] Polymers having such acid labile groups introduced therein shouldpreferably have a weight average molecular weight (Mw) of 3,000 to100,000. With a Mw of less than 3,000, polymers would perform poorly andoften lack heat resistance and film formability. Polymers with a Mw ofmore than 100,000 would be less soluble in a developer and a resistsolvent.

[0140] Where non-crosslinking acid labile groups are introduced, thepolymer should preferably have a dispersity (Mw/Mn) of up to 3.5,preferably up to 1.5. A polymer with a dispersity of more than 3.5 oftenresults in a low resolution. Where crosslinking acid labile groups areintroduced, the starting alkali-soluble resin should preferably have adispersity (Mw/Mn) of up to 1.5, and the dispersity is kept at 3 orlower even after protection with crosslinking acid labile groups. If thedispersity is higher than 3, dissolution, coating, storage stabilityand/or resolution is often poor.

[0141] To impart a certain function, suitable substituent groups may beintroduced into some of the phenolic hydroxyl and carboxyl groups on theacid labile group-protected polymer. Exemplary are substituent groupsfor improving adhesion to the substrate, non-acid-labile groups foradjusting dissolution in an alkali developer, and substituent groups forimproving etching resistance. Illustrative, non-limiting, substituentgroups include 2-hydroxyethyl, 2-hydroxypropyl, methoxymethyl,methoxycarbonyl, ethoxycarbonyl, methoxycarbonylmethyl,ethoxycarbonylmethyl, 4-methyl-2-oxo-4-oxoranyl,4-methyl-2-oxo-4-oxanyl, methyl, ethyl, propyl, n-butyl, sec-butyl,acetyl, pivaloyl, adamantyl, isoboronyl, and cyclohexyl.

[0142] In the resist composition of the invention, the above-describedresin is added in any desired amount, and usually 65 to 99 parts byweight, preferably 70 to 98 parts by weight per 100 parts by weight ofthe solids in the composition. The term “solids” is used to encompassall components in the resist composition excluding the solvent.

[0143] Illustrative examples of the sulfonyldiazomethane compounds offormulae (1) and (1a) as the photoacid generator (B) are as describedabove. Listing again, examples of bilaterally symmetricbissulfonyldiazomethane includebis(4-n-butylphenylsulfonyl)diazomethane,bis(4-n-pentylphenylsulfonyl)diazomethane,bis(4-n-hexylphenyl-sulfonyl)diazomethane,bis(4-n-heptylphenylsulfonyl)diazomethane,bis(4-n-octylphenylsulfonyl)diazomethane,bis(4-n-nonylphenylsulfonyl)diazomethane,bis(4-n-decylphenyl-sulfonyl)diazomethane,bis(4-n-undecylphenylsulfonyl)diazo-methane,bis(4-n-dodecylphenylsulfonyl)diazomethane,bis(4-(n-butyloxy)phenylsulfonyl)diazomethane,bis(4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(4-(n-hexyloxy)-phenylsulfonyl)diazomethane,bis(4-(n-heptyloxy)phenyl-sulfonyl)diazomethane,bis(4-(n-octyloxy)phenylsulfonyl)-diazomethane,bis(4-(n-nonyloxy)phenylsulfonyl)diazomethane,bis(4-(n-decyloxy)phenylsulfonyl)diazomethane,bis(4-(n-undecyloxy)phenylsulfonyl)diazomethane,bis(4-(n-dodecyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-butyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-heptyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-nonyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-decyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-undecyloxy)phenylsulfonyl)diazomethane,bis(3-methyl-4-(n-dodecyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-butyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-heptyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-nonyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-decyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-undecyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-dodecyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-butyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-heptyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-nonyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-decyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-undecyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-dodecyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-butyloxy)phenyl-sulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-heptyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-nonyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-decyloxy)phenylsulfonyl)diazomethane,bis(5-isopropyl-2-methyl-4-(n-undecyloxy)phenylsulfonyl)diazomethane,andbis(5-isopropyl-2-methyl-4-(n-dodecyloxy)phenylsulfonyl)diazomethane;

[0144] examples of bilaterally asymmetric sulfonyldiazomethane include(4-(n-hexyloxy)phenylsulfonyl)(methylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(tert-butylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(cyclohexylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(benzenesulfonyl)diazomethane,(4-(n-hexyloxy)-phenylsulfonyl)(p-toluenesulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(2,4-dimethylphenylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(4-tert-butylphenylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(-4-tert-butoxyphenylsulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(methylsulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(tert-butylsulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(cyclohexylsulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(benzenesulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(p-toluenesulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(2,4-dimethylphenylsulfonyl)diazomethane,(4-(n-octyloxy)phenylsulfonyl)(4-tert-butylphenylsulfonyl)diazomethane,and(4-(n-octyloxy)phenylsulfonyl)(4-tert-butoxyphenylsulfonyl)diazomethane;

[0145] examples of the sulfonylcarbonyldiazomethane include(4-(n-hexyloxy)phenylsulfonyl)(methylcarbonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(tert-butylcarbonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(cyclohexylcarbonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(benzoyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(p-toluenecarbonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(2,4-dimethyl-phenylcarbonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(4-tert-butylphenylcarbonyl)diazomethane,and(4-(n-hexyloxy)phenylsulfonyl)(4-tert-butoxyphenylcarbonyl)diazomethane,etc.

[0146] Of these, preferred are bis(4-n-hexylphenylsulfonyl)diazomethane,bis(4-n-pentylphenylsulfonyl)diazomethane,bis(4-n-octylphenylsulfonyl)diazomethane,bis(4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(4-(n-hexyloxy)-phenylsulfonyl)diazomethane,bis(4-(n-heptyloxy)phenyl-sulfonyl)diazomethane,bis(4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-pentyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-heptyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-octyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-hexyloxy)phenyl-sulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-heptyloxy)-phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-octyloxy)phenylsulfonyl)diazomethane,(4-(n-hexyloxy)phenyl-sulfonyl)(cyclohexylsulfonyl)diazomethane,(4-(n-hexyloxy)-phenylsulfonyl)(benzenesulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(p-toluenesulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(2,4-dimethylphenylsulfonyl)diazomethane,(4-(n-hexyloxy)phenylsulfonyl)(4-tert-butyl-phenylsulfonyl)diazomethane,and the like; and most preferred arebis(4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(2-methyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(2,5-dimethyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,bis(3,5-dimethyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane, andbis(2-methyl-5-isopropyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane.

[0147] In the chemical amplification resist composition, an appropriateamount of the sulfonyldiazomethane compound of formula (1) or (1a) addedis from more than 0 part to 10 parts by weight, and preferably from 1 to5 parts by weight, per 100 parts by weight of the solids in thecomposition. The sulfonyldiazomethane compound is used at least in anamount to generate a sufficient amount of acid to deblock acid labilegroups in the polymer. Too large amounts may excessively reduce thetransmittance of resist film, failing to form a rectangular pattern, andgive rise to problems of abnormal particles and deposits during resiststorage. The photoacid generators may be used alone or in admixture oftwo or more.

[0148] Component (C)

[0149] In one preferred embodiment, the resist composition furthercontains (C) a compound capable of generating an acid upon exposure tohigh energy radiation, that is, a second photoacid generator other thanthe sulfonyldiazomethane (B). Suitable second photoacid generatorsinclude sulfonium salts, iodonium salts, sulfonyldiazomethane andN-sulfonyloxyimide photoacid generators. Exemplary second photoacidgenerators are given below while they may be used alone or in admixtureof two or more.

[0150] Sulfonium salts are salts of sulfonium cations with sulfonates.Exemplary sulfonium cations include triphenylsulfonium,(4-tert-butoxyphenyl)diphenylsulfonium,bis(4-tert-butoxyphenyl)phenylsulfonium,tris(4-tert-butoxyphenyl)sulfonium,(3-tert-butoxyphenyl)diphenylsulfonium,bis(3-tert-butoxyphenyl)phenylsulfonium,tris(3-tert-butoxyphenyl)sulfonium,(3,4-di-tert-butoxyphenyl)diphenylsulfonium,bis(3,4-di-tert-butoxyphenyl)phenylsulfonium,tris(3,4-di-tert-butoxyphenyl)sulfonium,diphenyl(4-thiophenoxyphenyl)sulfonium,(4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium,tris(4-tert-butoxy-carbonylmethyloxyphenyl)sulfonium,(4-tert-butoxyphenyl)-bis(4-dimethylaminophenyl)sulfonium,tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium,dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium,4-methoxyphenyldimethylsulfonium, trimethylsulfonium,2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium,tribenzylsulfonium, diphenylmethylsulfonium, dimethylphenylsulfonium,and 2-oxo-2-phenylethylthiacyclopentanium. Exemplary sulfonates includetrifluoromethanesulfonate, nonafluorobutanesulfonate,heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,4-fluorobenzenesulfonate, mesitylenesulfonate,2,4,6-triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate,4-(4′-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate, and methanesulfonate. Sulfonium salts based oncombination of the foregoing examples are included.

[0151] Iodinium salts are salts of iodonium cations with sulfonates.Exemplary iodinium cations are aryliodonium cations includingdiphenyliodinium, bis(4-tert-butylphenyl)iodonium,4-tert-butoxyphenylphenyliodonium, and 4-methoxyphenylphenyliodonium.Exemplary sulfonates include trifluoromethanesulfonate,nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate,4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate,mesitylenesulfonate, 2,4,6-triisopropylbenzenesufonate,toluenesulfonate, benzenesulfonate,4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate, and methanesulfonate. Iodonium salts based oncombination of the foregoing examples are included.

[0152] Exemplary sulfonyldiazomethane compounds includebissulfonyldiazomethane compounds and sulfonylcarbonyldiazomethanecompounds such as bis(ethylsulfonyl)diazomethane,bis(1-methylpropylsulfonyl)diazomethane,bis(2-methylpropylsulfonyl)diazomethane,bis(1,1-dimethylethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane,bis(perfluoroisopropylsulfonyl)diazomethane,bis(phenylsulfonyl)diazomethane,bis(4-methylphenylsulfonyl)diazomethane,bis(2,4-dimethylphenylsulfonyl)diazomethane,bis(2-naphthylsulfonyl)diazomethane,bis(4-acetyloxyphenylsulfonyl)diazomethane,bis(4-methanesulfonyloxyphenylsulfonyl)diazomethane,bis(4-(4-toluenesulfonyloxy)phenylsulfonyl)diazomethane,4-methylphenylsulfonylbenzoyldiazomethane,tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane,2-naphthylsulfonylbenzoyldiazomethane,4-methylphenylsulfonyl-2-naphthoyldiazomethane,methylsulfonylbenzoyldiazomethane, andtert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane.

[0153] N-sulfonyloxyimide photoacid generators include combinations ofimide skeletons with sulfonates. Exemplary imide skeletons aresuccinimide, naphthalene dicarboxylic acid imide, phthalimide,cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acidimide, and 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid imide.Exemplary sulfonates include trifluoromethanesulfonate,nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate,4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate,mesitylenesulfonate, 2,4,6-triisopropylbenzenesulfonate,toluenesulfonate, benzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate, and methanesulfonate.

[0154] Benzoinsulfonate photoacid generators include benzoin tosylate,benzoin mesylate, and benzoin butanesulfonate.

[0155] Pyrogallol trisulfonate photoacid generators include pyrogallol,fluoroglycine, catechol, resorcinol, hydroquinone, in which all thehydroxyl groups are substituted with trifluoromethanesulfonate,nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate,4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate,toluenesulfonate, benzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate, and methanesulfonate.

[0156] Nitrobenzyl sulfonate photoacid generators include2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, and2,6-dinitrobenzyl sulfonate, with exemplary sulfonates includingtrifluoromethanesulfonate, nonafluorobutanesulfonate,heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,naphthalenesulfonate, camphorsulfonate, octanesulfonate,dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate. Alsouseful are analogous nitrobenzyl sulfonate compounds in which the nitrogroup on the benzyl side is substituted with a trifluoromethyl group.

[0157] Sulfone photoacid generators include bis(phenylsulfonyl)methane,bis(4-methylphenylsulfonyl)methane, bis(2-naphthylsulfonyl)methane,2,2-bis(phenylsulfonyl)propane, 2,2-bis(4-methylphenylsulfonyl)propane,2,2-bis(2-naphthylsulfonyl)propane,2-methyl-2-(p-toluenesulfonyl)propiophenone,2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, and2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one.

[0158] Photoacid generators in the form of glyoxime derivatives aredescribed in Japanese Patent No. 2,906,999 and JP-A 9-301948 and includebis-O-(p-toluenesulfonyl)-α-dimethylglyoxime,bis-O-(p-toluenesulfonyl)-α-diphenyl-glyoxime,bis-O-(p-toluenesulfonyl)-α-dicyclohexylglyoxime,bis-O-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime,bis-O-(n-butanesulfonyl)-α-dimethylglyoxime,bis-O-(n-butane-sulfonyl)-α-diphenylglyoxime,bis-O-(n-butanesulfonyl)-α-dicyclohexylglyoxime,bis-O-(methanesulfonyl)-α-dimethylglyoxime,bis-O-(trifluoromethanesulfonyl)-α-dimethylglyoxime,bis-O-(2,2,2-trifluoroethanesulfonyl)-α-dimethylglyoxime,bis-O-(10-camphorsulfonyl)-α-dimethylglyoxime,bis-O-(benzenesulfonyl)-α-dimethylglyoxime,bis-O-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime,bis-O-(p-trifluoromethylbenzenesulfonyl)-α-dimethylglyoxime,bis-O-(xylenesulfonyl)-α-dimethylglyoxime,bis-O-(trifluoromethanesulfonyl)-nioxime,bis-O-(2,2,2-trifluoroethanesulfonyl)-nioxime,bis-O-(10-camphorsulfonyl)-nioxime, bis-O-(benzenesulfonyl)-nioxime,bis-O-(p-fluorobenzenesulfonyl)-nioxime,bis-O-(p-trifluoromethylbenzenesulfonyl)-nioxime, andbis-O-(xylenesulfonyl)-nioxime.

[0159] Also included are the oxime sulfonates described in U.S. Pat. No.6,004,724, for example,(5-(4-toluenesulfonyl)oxyimino-5H-thiophen-2-ylidene)phenylacetonitrile,(5-(10-camphorsulfonyl)oxyimino-5H-thiophen-2-ylidene)phenylacetonitrile,(5-n-octanesulfonyloxyimino-5H-thiophen-2-ylidene)phenylacetonitrile,(5-(4-toluenesulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acetonitrile,(5-(10-camphorsulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acetonitrile,(5-n-octanesulfonyloxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acetonitrile,etc.

[0160] Also included are the oxime sulfonates described in U.S. Pat. No.6,261,738 and JP-A 2000-314956, for example,2,2,2-trifluoro-1-phenyl-ethanone oxime-O-methylsulfonate;2,2,2-trifluoro-1-phenyl-ethanone oxime-O-(10-camphorylsulfonate);2,2,2-trifluoro-1-phenyl-ethanone oxime-O-(4-methoxyphenylsulfonate);2,2,2-trifluoro-1-phenyl-ethanone oxime-O-(1-naphthylsulfonate);2,2,2-trifluoro-1-phenyl-ethanone oxime-O-(2-naphthylsulfonate);2,2,2-trifluoro-1-phenyl-ethanoneoxime-O-(2,4,6-trimethylphenylsulfonate);2,2,2-trifluoro-1-(4-methylphenyl)-ethanoneoxime-O-(10-camphorylsulfonate);2,2,2-trifluoro-1-(4-methylphenyl)-ethanone oxime-O-(methylsulfonate);2,2,2-trifluoro-1-(2-methylphenyl)-ethanoneoxime-O-(10-camphorylsulfonate);2,2,2-trifluoro-1-(2,4-dimethylphenyl)-ethanoneoxime-O-(10-camphorylsulfonate);2,2,2-trifluoro-1-(2,4-dimethylphenyl)-ethanoneoxime-O-(1-naphthylsulfonate);2,2,2-trifluoro-1-(2,4-dimethylphenyl)-ethanoneoxime-O-(2-naphthylsulfonate);2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)-ethanoneoxime-O-(10-camphorylsulfonate);2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)-ethanoneoxime-O-(1-naphthylsulfonate);2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)-ethanoneoxime-O-(2-naphthylsulfonate); 2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone oxime-O-methylsulfonate;2,2,2-trifluoro-1-(4-methylthiophenyl)-ethanone oxime-O-methylsulfonate;2,2,2-trifluoro-1-(3,4-dimethoxyphenyl)-ethanoneoxime-O-methylsulfonate; 2,2,3,3,4,4,4-heptafluoro-1-phenyl-butanoneoxime-O-(10-camphorylsulfonate); 2,2,2-trifluoro-1-(phenyl)-ethanoneoxime-O-methylsulfonate; 2,2,2-trifluoro-1-(phenyl)-ethanoneoxime-O-10-camphorylsulfonate; 2,2,2-trifluoro-1-(phenyl)-ethanoneoxime-O-(4-methoxyphenyl)sulfonate; 2,2,2-trifluoro-1-(phenyl)-ethanoneoxime-O-(1-naphthyl)sulfonate; 2,2,2-trifluoro-1-(phenyl)-ethanoneoxime-O-(2-naphthyl)sulfonate; 2,2,2-trifluoro-1-(phenyl)-ethanoneoxime-O-(2,4,6-trimethylphenyl)sulfonate;2,2,2-trifluoro-1-(4-methylphenyl)-ethanoneoxime-O-(10-camphoryl)sulfonate;2,2,2-trifluoro-1-(4-methylphenyl)-ethanone oxime-O-methylsulfonate;2,2,2-trifluoro-1-(2-methylphenyl)-ethanoneoxime-O-(10-camphoryl)sulfonate;2,2,2-trifluoro-1-(2,4-dimethylphenyl)-ethanoneoxime-O-(1-naphthyl)sulfonate;2,2,2-trifluoro-1-(2,4-dimethylphenyl)-ethanoneoxime-O-(2-naphthyl)sulfonate;2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)-ethanoneoxime-O-(10-camphoryl)sulfonate;2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)-ethanoneoxime-O-(1-naphthyl)sulfonate;2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)-ethanoneoxime-O-(2-naphthyl)sulfonate;2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime-O-methylsulfonate;2,2,2-trifluoro-1-(4-thiomethylphenyl)-ethanone oxime-O-methylsulfonate;2,2,2-trifluoro-1-(3,4-dimethoxyphenyl)-ethanoneoxime-O-methylsulfonate; 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanoneoxime-O-(4-methylphenyl)sulfonate;2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanoneoxime-O-(4-methoxyphenyl)sulfonate;2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanoneoxime-O-(4-dodecylphenyl)sulfonate;2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime-O-octylsulfonate;2,2,2-trifluoro-1-(4-thiomethylphenyl)-ethanoneoxime-O-(4-methoxyphenyl)sulfonate;2,2,2-trifluoro-1-(4-thiomethylphenyl)-ethanoneoxime-O-(4-dodecylphenyl)sulfonate;2,2,2-trifluoro-1-(4-thiomethylphenyl)-ethanone oxime-O-octylsulfonate;2,2,2-trifluoro-1-(4-thiomethylphenyl)-ethanoneoxime-O-(2-naphthyl)sulfonate;2,2,2-trifluoro-1-(2-methylphenyl)-ethanone oxime-O-methylsulfonate;2,2,2-trifluoro-1-(4-methylphenyl)ethanone oxime-O-phenylsulfonate;2,2,2-trifluoro-1-(4-chlorophenyl)-ethanone oxime-O-phenylsulfonate;2,2,3,3,4,4,4-heptafluoro-1-(phenyl)-butanoneoxime-O-(10-camphoryl)sulfonate; 2,2,2-trifluoro-1-naphthyl-ethanoneoxime-O-methylsulfonate; 2,2,2-trifluoro-2-naphthyl-ethanoneoxime-O-methylsulfonate; 2,2,2-trifluoro-1-[4-benzylphenyl]-ethanoneoxime-O-methylsulfonate;2,2,2-trifluoro-1-[4-(phenyl-1,4-dioxa-but-1-yl)phenyl]-ethanoneoxime-O-methylsulfonate; 2,2,2-trifluoro-1-naphthyl-ethanoneoxime-O-propylsulfonate; 2,2,2-trifluoro-2-naphthyl-ethanoneoxime-O-propylsulfonate; 2,2,2-trifluoro-1-[4-benzylphenyl]-ethanoneoxime-O-propylsulfonate;2,2,2-trifluoro-1-[4-methylsulfonylphenyl]-ethanoneoxime-O-propylsulfonate;1,3-bis[1-(4-phenoxyphenyl)-2,2,2-trifluoroethanoneoxime-O-sulfonyl]phenyl;2,2,2-trifluoro-1-[4-methylsulfonyloxyphenyl]-ethanoneoxime-O-propylsulfonate;2,2,2-trifluoro-1-[4-methylcarbonyloxyphenyl]-ethanoneoxime-O-propylsulfonate;2,2,2-trifluoro-1-[6H,7H-5,8-dioxonaphth-2-yl]-ethanoneoxime-O-propylsulfonate;2,2,2-trifluoro-1-[4-methoxycarbonylmethoxyphenyl]-ethanoneoxime-O-propylsulfonate;2,2,2-trifluoro-1-[4-(methoxycarbonyl)-(4-amino-1-oxa-pent-1-yl)-phenyl]-ethanoneoxime-O-propylsulfonate;2,2,2-trifluoro-1-[3,5-dimethyl-4-ethoxyphenyl]-ethanoneoxime-O-propylsulfonate; 2,2,2-trifluoro-1-[4-benzyloxyphenyl]-ethanoneoxime-O-propylsulfonate; 2,2,2-trifluoro-1-[2-thiophenyl]-ethanoneoxime-O-propylsulfonate; and2,2,2-trifluoro-1-[1-dioxa-thiophen-2-yl)]-ethanoneoxime-O-propylsulfonate.

[0161] Also included are the oxime sulfonates described in JP-A 9-95479and JP-A 9-230588 and the references cited therein, for example,α-(p-toluenesulfonyloxyimino)-phenylacetonitrile,α-(p-chlorobenzenesulfonyloxyimino)-phenylacetonitrile,α-(4-nitrobenzenesulfonyloxyimino)-phenylacetonitrile,α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino)-phenylacetonitrile,α-(benzenesulfonyloxyimino)-4-chlorophenylacetonitrile,α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile,α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile,α-(benzenesulfonyloxyimino)-4-methoxyphenylacetonitrile,α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile,α-(benzenesulfonyloxyimino)-2-thienylacetonitrile,α-(4-dodecylbenzenesulfonyloxyimino)-phenylacetonitrile,α-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile,α-[(dodecylbenzenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile,α-(tosyloxyimino)-3-thienylacetonitrile,α-(methylsulfonyloxyimino)-1-cyclopentenylacetonitrile,α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile,α-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile,α-(n-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile,α-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile,α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, andα-(n-butylsulfonyloxyimino)-1-cyclohexenylacetonitrile.

[0162] Suitable bisoxime sulfonates include those described in JP-A9-208554, for example,bis(α-(4-toluenesulfonyloxy)imino)-p-phenylenediacetonitrile,bis(α-(benzenesulfonyloxy)imino)-p-phenylenediacetonitrile,bis(α-(methanesulfonyloxy)imino)-p-phenylenediacetonitrile,bis(α-(butanesulfonyloxy)imino)-p-phenylenediacetonitrile,bis(α-(10-camphorsulfonyloxy)imino)-p-phenylenediacetonitrile,bis(a-(4-toluenesulfonyloxy)imino)-p-phenylenediacetonitrile,bis(α-(trifluoromethanesulfonyloxy)imino)-p-phenylenediacetonitrile, bis(α-(4-methoxybenzenesulfonyloxy)imino)-p-phenylenediacetonitrile,bis(α-(4-toluenesulfonyloxy)imino)-m-phenylenediacetonitrile,bis(α-(benzenesulfonyloxy)imino)-m-phenylenediacetonitrile,bis(α-(methanesulfonyloxy)imino)-m-phenylenediacetonitrile,bis(α-(butanesulfonyloxy)imino)-m-phenylenediacetonitrile,bis(α-(10-camphorsulfonyloxy)imino)-m-phenylenediacetonitrile,bis(α-(4-toluenesulfonyloxy)imino)-m-phenylenediacetonitrile,bis(α-(trifluoromethanesulfonyloxy)imino)-m-phenylenediacetonitrile,bis(α-(4-methoxybenzenesulfonyloxy)imino)-m-phenylene-diacetonitrile,etc.

[0163] Of these, preferred photoacid generators are sulfonium salts,bissulfonyldiazomethanes, N-sulfonyloxyimides and glyoxime derivatives.More preferred photoacid generators are sulfonium salts,bissulfonyldiazomethanes, and N-sulfonyloxyimides. Typical examplesinclude triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumcamphorsulfonate, triphenylsulfonium pentafluorobenzenesulfonate,triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium4-(4′-toluenesulfonyloxy)benzenesulfonate, triphenylsulfonium2,4,6-triisopropylbenzenesulfonate, 4-tert-butoxyphenyldiphenylsulfoniump-toluenesulfonate, 4-tert-butoxyphenyldiphenylsulfoniumcamphorsulfonate, 4-tert-butoxyphenyldiphenylsulfonium4-(4′-toluenesulfonyloxy)benzenesulfonate, tris(4-methylphenyl)sulfoniumcamphorsulfonate, tris(4-tert-butylphenyl)sulfonium camphorsulfonate,bis(tert-butylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane,bis(2,4-dimethylphenylsulfonyl)diazomethane,bis(4-tert-butylphenylsulfonyl)diazomethane,N-camphorsulfonyloxy-5-norbornene-2,3-carboxylic acid imide, andN-p-toluenesulfonyloxy-5-norbornene-2,3-carboxylic acid imide.

[0164] In the resist composition comprising the sulfonyldiazomethane offormula (1) or (1a) as the first photoacid generator according to theinvention, the second photoacid generator (C) may be used in any desiredamount as long as it does not compromise the effects of thesulfonyldiazomethane of formula (1) or (1a). An appropriate amount ofthe second photoacid generator (C) is 0 to 10 parts, and especially 0 to5 parts by weight per 100 parts by weight of the solids in thecomposition. Too high a proportion of the second photoacid generator (C)may give rise to problems of degraded resolution and foreign matter upondevelopment and resist film peeling. The second photoacid generators maybe used alone or in admixture of two or more. The transmittance of theresist film can be controlled by using a (second) photoacid generatorhaving a low transmittance at the exposure wavelength and adjusting theamount of the photoacid generator added.

[0165] In the resist composition comprising the sulfonyldiazomethane asthe photoacid generator according to the invention, there may be added acompound which is decomposed with an acid to generate an acid, that is,acid-propagating compound. For these compounds, reference should be madeto J. Photopolym. Sci. and Tech., 8, 43-44, 45-46 (1995), and ibid., 9,29-30 (1996).

[0166] Examples of the acid-propagating compound includetert-butyl-2-methyl-2-tosyloxymethyl acetoacetate and2-phenyl-2-(2-tosyloxyethyl)-1,3-dioxolane, but are not limited thereto.Of well-known photoacid generators, many of those compounds having poorstability, especially poor thermal stability exhibit an acid-propagatingcompound-like behavior.

[0167] In the resist composition comprising the sulfonyldiazomethane asthe photoacid generator according to the invention, an appropriateamount of the acid-propagating compound is up to 2 parts, and especiallyup to 1 part by weight per 100 parts by weight of the solids in thecomposition. Excessive amounts of the acid-propagating compound makesdiffusion control difficult, leading to degradation of resolution andpattern configuration.

[0168] Component (D)

[0169] The basic compound used as component (D) is preferably a compoundcapable of suppressing the rate of diffusion when the acid generated bythe photoacid generator diffuses within the resist film. The inclusionof this type of basic compound holds down the rate of acid diffusionwithin the resist film, resulting in better resolution. In addition, itsuppresses changes in sensitivity following exposure and reducessubstrate and environment dependence, as well as improving the exposurelatitude and the pattern profile.

[0170] Examples of basic compounds include primary, secondary, andtertiary aliphatic amines, mixed amines, aromatic amines, heterocyclicamines, carboxyl group-bearing nitrogenous compounds, sulfonylgroup-bearing nitrogenous compounds, hydroxyl group-bearing nitrogenouscompounds, hydroxyphenyl group-bearing nitrogenous compounds, alcoholicnitrogenous compounds, amide derivatives, and imide derivatives.

[0171] Examples of suitable primary aliphatic amines include ammonia,methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,isobutylamine, sec-butylamine, tert-butylamine, pentylamine,tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine,heptylamine, octylamine, nonylamine, decylamine, dodecylamine,cetylamine, methylenediamine, ethylenediamine, andtetraethylenepentamine. Examples of suitable secondary aliphatic aminesinclude dimethylamine, diethylamine, di-n-propylamine, diisopropylamine,di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine,dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine,dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine,N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, andN,N-dimethyltetraethylenepentamine. Examples of suitable tertiaryaliphatic amines include trimethylamine, triethylamine,tri-n-propylamine, triisopropylamine, tri-n-butylamine,triisobutylamine, tri-sec-butylamine, tripentylamine,tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine,trioctylamine, trinonylamine, tridecylamine, tridodecylamine,tricetylamine, N,N,N′,N′-tetramethylmethylenediamine,N,N,N′,N′-tetramethylethylenediamine, andN,N,N′,N′-tetramethyltetraethylenepentamine.

[0172] Examples of suitable mixed amines include dimethylethylamine,methylethylpropylamine, benzylamine, phenethylamine, andbenzyldimethylamine. Examples of suitable aromatic and heterocyclicamines include aniline derivatives (e.g., aniline, N-methylaniline,N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline,3-methylaniline, 4-methylaniline, ethylaniline, propylaniline,trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline,2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, andN,N-dimethyltoluidine), diphenyl(p-tolyl)amine, methyldiphenylamine,triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene,pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole,2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole), oxazolederivatives (e.g., oxazole and isooxazole), thiazole derivatives (e.g.,thiazole and isothiazole), imidazole derivatives (e.g., imidazole,4-methylimidazole, and 4-methyl-2-phenylimidazole), pyrazolederivatives, furazan derivatives, pyrroline derivatives (e.g., pyrrolineand 2-methyl-1-pyrroline), pyrrolidine derivatives (e.g., pyrrolidine,N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone),imidazoline derivatives, imidazolidine derivatives, pyridine derivatives(e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine,butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine,trimethylpyridine, triethylpyridine, phenylpyridine,3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine,benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine,1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine,2-(1-ethylpropyl)pyridine, aminopyridine, and dimethylaminopyridine),pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives,pyrazoline derivatives, pyrazolidine derivatives, piperidinederivatives, piperazine derivatives, morpholine derivatives, indolederivatives, isoindole derivatives, 1H-indazole derivatives, indolinederivatives, quinoline derivatives (e.g., quinoline and3-quinolinecarbonitrile), isoquinoline derivatives, cinnolinederivatives, quinazoline derivatives, quinoxaline derivatives,phthalazine derivatives, purine derivatives, pteridine derivatives,carbazole derivatives, phenanthridine derivatives, acridine derivatives,phenazine derivatives, 1,10-phenanthroline derivatives, adeninederivatives, adenosine derivatives, guanine derivatives, guanosinederivatives, uracil derivatives, and uridine derivatives.

[0173] Examples of suitable carboxyl group-bearing nitrogenous compoundsinclude aminobenzoic acid, indolecarboxylic acid, and amino acidderivatives (e.g. nicotinic acid, alanine, alginine, aspartic acid,glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine,methionine, phenylalanine, threonine, lysine,3-aminopyrazine-2-carboxylic acid, and methoxyalanine). Examples ofsuitable sulfonyl group-bearing nitrogenous compounds include3-pyridinesulfonic acid and pyridinium p-toluenesulfonate. Examples ofsuitable hydroxyl group-bearing nitrogenous compounds, hydroxyphenylgroup-bearing nitrogenous compounds, and alcoholic nitrogenous compoundsinclude 2-hydroxypyridine, aminocresol, 2,4-quinolinediol,3-indolemethanol hydrate, monoethanolamine, diethanolamine,triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine,triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol,3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine,2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine,1-[2-(2-hydroxyethoxy)ethyl]-piperazine, piperidine ethanol,1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone,3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol,8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridine ethanol, N-(2-hydroxyethyl)phthalimide, andN-(2-hydroxyethyl)isonicotinamide. Examples of suitable amidederivatives include formamide, N-methylformamide, N,N-dimethylformamide,acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, andbenzamide. Suitable imide derivatives include phthalimide, succinimide,and maleimide.

[0174] In addition, basic compounds of the following general formula(D1) may also be included alone or in admixture.

N(X′)_(W)(Y)_(3-W)   D1

[0175] In the formula, w is equal to 1, 2 or 3; Y is independentlyhydrogen or a straight, branched or cyclic alkyl group of 1 to 20 carbonatoms which may contain a hydroxyl group or ether structure; and X′ isindependently selected from groups of the following general formulas(X′1) to (X′3), and two or three X′ may bond together to form a ring.

[0176] In the formulas, R³⁰⁰, R³⁰² and R³⁰⁵ are independently straightor branched alkylene groups of 1 to 4 carbon atoms; R³⁰¹, R³⁰⁴ and R³⁰⁶are independently hydrogen, straight, branched or cyclic alkyl groups of1 to 20 carbon atoms, which may contain at least one hydroxyl group,ether structure, ester structure or lactone ring; and R³⁰³ is a singlebond or a straight or branched alkylene group of 1 to 4 carbon atoms.

[0177] Illustrative examples of the basic compounds of formula (D1)include tris(2-methoxymethoxyethyl)amine,tris{2-(2-methoxyethoxy)ethyl}amine,tris{2-(2-methoxy-ethoxymethoxy)ethyl}amine,tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl)amine,tris{2-(1-ethoxypropoxy)ethyl}amine,tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine,4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane,4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane,1,4,10,13-tetraoxa-7,16-diazabicyclo-octadecane, 1-aza-12-crown-4,1-aza-15-crown-5, 1-aza-18-crown-6, tris(2-formyloxyethyl)amine,tris(2-acetoxyethyl)amine, tris(2-propionyloxyethyl)amine,tris(2-butyryloxyethyl)amine, tris(2-isobutyryloxyethyl)amine,tris(2-valeryloxyethyl)amine, tris(2-pivaloyloxyethyl)amine,N,N-bis(2-acetoxyethyl)-2-(acetoxyacetoxy)ethylamine,tris(2-methoxycarbonyloxyethyl)amine,tris(2-tert-butoxycarbonyloxyethyl)amine,tris[2-(2-oxopropoxy)ethyl]amine,tris[2-(methoxycarbonylmethyl)oxyethyl]amine,tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine,tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine,tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine,N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine,N,N-bis(2-hydroxy-ethyl)-2-(ethoxycarbonyl)ethylamine,N,N-bis(2-acetoxy-ethyl)-2-(ethoxycarbonyl)ethylamine,N,N-bis(2-hydroxy-ethyl)-2-(2-methoxyethoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine,N,N-bis(2-acetoxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine,N,N-bis(2-hydroxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine,N,N-bis(2-acetoxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine,N,N-bis(2-hydroxyethyl)-2-(4-hydroxybutoxycarbonyl)ethylamine,N,N-bis(2-formyloxyethyl)-2-(4-formyloxybutoxycarbonyl)ethylamine,N,N-bis(2-formyloxyethyl)-2-(2-formyloxyethoxycarbonyl)ethylamine,N,N-bis(2-methoxyethyl)-2-(methoxycarbonyl)ethylamine,N-(2-hydroxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine,N-(2-acetoxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine,N-(2-hydroxyethyl)-bis[2-(ethoxycarbonyl)ethyl]amine,N-(2-acetoxyethyl)-bis[2-(ethoxycarbonyl)ethyl]amine,N-(3-hydroxy-1-propyl)-bis[2-(methoxycarbonyl)ethyl]amine,N-(3-acetoxy-1-propyl)-bis[2-(methoxycarbonyl)ethyl]amine,N-(2-methoxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine,N-butyl-bis[2-(methoxycarbonyl)ethyl]amine,N-butyl-bis[2-(2-methoxyethoxycarbonyl)ethyl]amine,N-methyl-bis(2-acetoxyethyl)amine, N-ethyl-bis(2-acetoxyethyl)amine,N-methyl-bis(2-pivaloyloxyethyl)amine,N-ethyl-bis[2-(methoxycarbonyloxy)ethyl]amine,N-ethyl-bis[2-(tert-butoxycarbonyloxy)ethyl]amine,tris(methoxycarbonylmethyl)amine, tris(ethoxycarbonylmethyl)amine,N-butyl-bis(methoxycarbonylmethyl)amine,N-hexyl-bis(methoxycarbonylmethyl)amine, andβ-(diethylamino)-δ-valerolactone.

[0178] Also useful are one or more of cyclic structure-bearing basiccompounds having the following general formula (D2).

[0179] Herein X′ is as defined above, and R³⁰⁷ is a straight or branchedalkylene group of 2 to 20 carbon atoms which may contain one or morecarbonyl groups, ether structures, ester structures or sulfidestructures.

[0180] Illustrative examples of the cyclic structure-bearing basiccompounds having formula (D2) include1-[2-(methoxymethoxy)ethyl]pyrrolidine,1-[2-(methoxymethoxy)ethyl]piperidine,4-[2-(methoxymethoxy)ethyl]morpholine,1-[2-[(2-methoxyethoxy)methoxy]ethyl]pyrrolidine,1-[2-[(2-methoxyethoxy)methoxy]ethyl]piperidine,4-[2-[(2-methoxyethoxy)methoxy]ethyl]morpholine, 2-(1-pyrrolidinyl)ethylacetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate,2-(1-pyrrolidinyl)ethyl formate, 2-piperidinoethyl propionate,2-morpholinoethyl acetoxyacetate, 2-(1-pyrrolidinyl)ethylmethoxyacetate, 4-[2-(methoxycarbonyloxy)ethyl]morpholine,1-[2-(t-butoxycarbonyloxy)ethyl]piperidine,4-[2-(2-methoxyethoxycarbonyloxy)ethyl]morpholine, methyl3-(1-pyrrolidinyl)propionate, methyl 3-piperidinopropionate, methyl3-morpholinopropionate, methyl 3-(thiomorpholino)propionate, methyl2-methyl-3-(1-pyrrolidinyl)propionate, ethyl 3-morpholinopropionate,methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl3-(1-pyrrolidinyl)propionate, 2-acetoxyethyl 3-morpholinopropionate,2-oxotetrahydrofuran-3-yl 3-(1-pyrrolidinyl)propionate,tetrahydrofurfuryl 3-morpholinopropionate, glycidyl3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate,2-(2-methoxyethoxy)ethyl 3-(1-pyrrolidinyl)propionate, butyl3-morpholinopropionate, cyclohexyl 3-piperidinopropionate,α-(1-pyrrolidinyl)methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone,β-morpholino-δ-valerolactone, methyl 1-pyrrolidinylacetate, methylpiperidinoacetate, methyl morpholinoacetate, methylthiomorpholinoacetate, ethyl 1-pyrrolidinylacetate, and 2-methoxyethylmorpholinoacetate.

[0181] Also, one or more of cyano-bearing basic compounds having thefollowing general formulae (D3) to (D6) may be blended.

[0182] Herein, X′, R³⁰⁷ and w are as defined above, and R³⁰⁸ and R³⁰⁹each are independently a straight or branched alkylene group of 1 to 4carbon atoms.

[0183] Illustrative examples of the cyano-bearing basic compounds havingformulae (D3) to (D6) include 3-(diethylamino)propiononitrile,N,N-bis(2-hydroxyethyl)-3-aminopropiononitrile,N,N-bis(2-acetoxyethyl)-3-aminopropiononitrile,N,N-bis(2-formyloxyethyl)-3-aminopropiononitrile,N,N-bis(2-methoxyethyl)-3-aminopropiononitrile,N,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropiononitrile, methylN-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropionate, methylN-(2-cyanoethyl)-N-(2-hydroxyethyl)-3-aminopropionate, methylN-(2-acetoxyethyl)-N-(2-cyanoethyl)-3-aminopropionate,N-(2-cyanoethyl)-N-ethyl-3-aminopropiononitrile,N-(2-cyanoethyl)-N-(2-hydroxyethyl)-3-aminopropiononitrile,N-(2-acetoxyethyl)-N-(2-cyanoethyl)-3-aminopropiononitrile,N-(2-cyanoethyl)-N-(2-formyloxyethyl)-3-aminopropiononitrile,N-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropiononitrile,N-(2-cyanoethyl)-N-[2-(methoxymethoxy)ethyl]-3-aminopropiononitrile,N-(2-cyanoethyl)-N-(3-hydroxy-1-propyl)-3-aminopropiononitrile,N-(3-acetoxy-1-propyl)-N-(2-cyanoethyl)-3-aminopropiononitrile,N-(2-cyanoethyl)-N-(3-formyloxy-1-propyl)-3-aminopropiononitrile,N-(2-cyanoethyl)-N-tetrahydrofurfuryl-3-aminopropiononitrile,N,N-bis(2-cyanoethyl)-3-aminopropiononitrile, diethylaminoacetonitrile,N,N-bis(2-hydroxyethyl)aminoacetonitrile,N,N-bis(2-acetoxyethyl)aminoacetonitrile,N,N-bis(2-formyloxyethyl)aminoacetonitrile,N,N-bis(2-methoxyethyl)aminoacetonitrile,N,N-bis[2-(methoxymethoxy)ethyl]aminoacetonitrile, methylN-cyanomethyl-N-(methoxyethyl)-3-aminopropionate, methylN-cyanomethyl-N-(2-hydroxyethyl)-3-aminopropionate, methylN-(2-acetoxyethyl)-N-cyanomethyl-3-aminopropionate,N-cyanomethyl-N-(2-hydroxyethyl)aminoacetonitrile,N-(2-acetoxyethyl)-N-(cyanomethyl)aminoacetonitrile,N-cyanomethyl-N-(2-formyloxyethyl)aminoacetonitrile,N-cyanomethyl-N-(2-methoxyethyl)aminoacetonitrile,N-cyanomethyl-N-[2-(methoxymethoxy)ethyl)aminoacetonitrile,N-cyanomethyl-N-(3-hydroxy-1-propyl)aminoacetonitrile,N-(3-acetoxy-1-propyl)-N-(cyanomethyl)aminoacetonitrile,N-cyanomethyl-N-(3-formyloxy-1-propyl)aminoacetonitrile,N,N-bis(cyanomethyl)aminoacetonitrile, 1-pyrrolidinepropiononitrile,1-piperidinepropiononitrile, 4-morpholinepropiononitrile,1-pyrrolidineacetonitrile, 1-piperidineacetonitrile,4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate,cyanomethyl N,N-bis(2-hydroxyethyl)-3-aminopropionate, cyanomethylN,N-bis(2-acetoxyethyl)-3-aminopropionate, cyanomethylN,N-bis(2-formyloxyethyl)-3-aminopropionate, cyanomethylN,N-bis(2-methoxyethyl)-3-aminopropionate, cyanomethylN,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropionate, 2-cyanoethyl3-diethylaminopropionate, 2-cyanoethylN,N-bis(2-hydroxyethyl)-3-aminopropionate, 2-cyanoethylN,N-bis(2-acetoxyethyl)-3-aminopropionate, 2-cyanoethylN,N-bis(2-formyloxyethyl)-3-aminopropionate, 2-cyanoethylN,N-bis(2-methoxyethyl)-3-aminopropionate, 2-cyanoethylN,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropionate, cyanomethyl1-pyrrolidinepropionate, cyanomethyl 1-piperidinepropionate, cyanomethyl4-morpholinepropionate, 2-cyanoethyl 1-pyrrolidinepropionate,2-cyanoethyl 1-piperidinepropionate, and 2-cyanoethyl4-morpholinepropionate.

[0184] The basic compounds may be used alone or in admixture of two ormore. The basic compound is preferably formulated in an amount of 0 to 2parts, and especially 0.01 to 1 part by weight, per 100 parts by weightof the solids in the resist composition. The use of more than 2 parts ofthe basis compound would result in too low a sensitivity.

[0185] Component (E)

[0186] Illustrative, non-limiting, examples of the organic acidderivatives (E) include phenol, cresol, catechol, resorcinol,pyrogallol, fluoroglycin, bis(4-hydroxyphenyl)methane,2,2-bis(4′-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone,1,1,1-tris(4′-hydroxyphenyl)ethane, 1,1,2-tris(4′-hydroxyphenyl)ethane,hydroxybenzophenone, 4-hydroxyphenylacetic acid, 3-hydroxyphenylaceticacid, 2-hydroxyphenylacetic acid, 3-(4-hydroxyphenyl)propionic acid,3-(2-hydroxyphenyl)propionic acid, 2,5-dihydroxyphenylacetic acid,3,4-dihydroxyphenylacetic acid, 1,2-phenylenediacetic acid,1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid,1,2-phenylenedioxydiacetic acid, 1,4-phenylenedipropanoic acid, benzoicacid, salicylic acid, 4,4-bis(4′-hydroxyphenyl)valeric acid,4-tert-butoxyphenylacetic acid, 4-(4-hydroxyphenyl)butyric acid,3,4-dihydroxymandelic acid, and 4-hydroxymandelic acid. Of these,salicylic acid and 4,4-bis(4′-hydroxyphenyl)valeric acid are preferred.They may be used alone or in admixture of two or more.

[0187] In the resist composition comprising the sulfonyldiazomethane asthe photoacid generator according to the invention, the organic acidderivative is preferably formulated in an amount of up to 5 parts, andespecially up to 1 part by weight, per 100 parts by weight of the solidsin the resist composition. The use of more than 5 parts of the organicacid derivative would result in too low a resolution. Depending on thecombination of the other components in the resist composition, theorganic acid derivative may be omitted.

[0188] Component (F)

[0189] Component (F) is an organic solvent. Illustrative, non-limiting,examples include butyl acetate, amyl acetate, cyclohexyl acetate,3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone,cyclohexanone, cyclopentanone, 3-ethoxyethyl propionate, 3-ethoxymethylpropionate, 3-methoxymethyl propionate, methyl acetoacetate, ethylacetoacetate, diacetone-alcohol, methyl pyruvate, ethyl pyruvate,propylene glycol monomethyl ether, propylene glycol monoethyl ether,propylene glycol monomethyl ether propionate, propylene glycol monoethylether propionate, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, diethylene glycol monomethyl ether, diethylene glycolmonoethyl ether, 3-methyl-3-methoxybutanol, N-methyl-pyrrolidone,dimethyl sulfoxide, γ-butyrolactone, propylene glycol methyl etheracetate, propylene glycol ethyl ether acetate, propylene glycol propylether acetate, methyl lactate, ethyl lactate, propyl lactate, andtetramethyl sulfone. Of these, the propylene glycol alkyl ether acetatesand alkyl lactates are especially preferred. The solvents may be usedalone or in admixture of two or more. An exemplary useful solventmixture is a mixture of a propylene glycol alkyl ether acetate and analkyl lactate. It is noted that the alkyl groups of the propylene glycolalkyl ether acetates are preferably those of 1 to 4 carbon atoms, forexample, methyl, ethyl and propyl, with methyl and ethyl beingespecially preferred. Since the propylene glycol alkyl ether acetatesinclude 1,2- and 1,3-substituted ones, each includes three isomersdepending on the combination of substituted positions, which may be usedalone or in admixture.

[0190] When the propylene glycol alkyl ether acetate is used as thesolvent, it preferably accounts for at least 50% by weight of the entiresolvent. Also when the alkyl lactate is used as the solvent, itpreferably accounts for at least 50% by weight of the entire solvent.When a mixture of propylene glycol alkyl ether acetate and alkyl lactateis used as the solvent, that mixture preferably accounts for at least50% by weight of the entire solvent. In this solvent mixture, it isfurther preferred that the propylene glycol alkyl ether acetate is 60 to95% by weight and the alkyl lactate is 40 to 5% by weight. A lowerproportion of the propylene glycol alkyl ether acetate would invite aproblem of inefficient coating whereas a higher proportion thereof wouldprovide insufficient dissolution and allow for particle and foreignmatter formation. A lower proportion of the alkyl lactate would provideinsufficient dissolution and cause the problem of many particles andforeign matter whereas a higher proportion thereof would lead to acomposition which has a too high viscosity to apply and loses storagestability.

[0191] The solvent is preferably used in an amount of 300 to 2,000 partsby weight, especially 400 to 1,000 parts by weight per 100 parts byweight of the solids in the resist composition. The solventconcentration is not limited thereto as long as a film can be formed byexisting methods.

[0192] Component (G)

[0193] In one preferred embodiment, the resist composition furthercontains (G) a compound with a molecular weight of up to 3,000 whichchanges its solubility in an alkaline developer under the action of anacid, that is, a dissolution inhibitor. Typically, a compound obtainedby partially or entirely substituting acid labile substituents on aphenol or carboxylic acid derivative having a molecular weight of up to2,500 is added as the dissolution inhibitor.

[0194] Examples of the phenol or carboxylic acid derivative having amolecular weight of up to 2,500 include bisphenol A, bisphenol H,bisphenol S, 4,4-bis(4′-hydroxyphenyl)valeric acid,tris(4-hydroxyphenyl)methane, 1,1,1-tris(4′-hydroxyphenyl)ethane,1,1,2-tris(4′-hydroxyphenyl)ethane, phenolphthalein, andthymolphthalein. The acid labile substituents are the same as thoseexemplified as the acid labile groups in the polymer.

[0195] Illustrative, non-limiting, examples of the dissolutioninhibitors which are useful herein includebis(4-(2′-tetrahydropyranyloxy)phenyl)methane,bis(4-(2′-tetrahydrofuranyloxy)phenyl)methane,bis(4-tert-butoxyphenyl)methane,bis(4-tert-butoxycarbonyloxyphenyl)methane,bis(4-tert-butoxycarbonylmethyloxyphenyl)methane,bis(4-(1′-ethoxyethoxy)phenyl)methane,bis(4-(1′-ethoxypropyloxy)phenyl)methane,2,2-bis(4′-(2″-tetrahydropyranyloxy))propane,2,2-bis(4′-(2″-tetrahydrofuranyloxy)phenyl)propane,2,2-bis(4′-tert-butoxyphenyl)propane,2,2-bis(4′-tert-butoxycarbonyloxyphenyl)propane,2,2-bis(4-tert-butoxycarbonylmethyloxyphenyl)propane,2,2-bis(4′-(1″-ethoxyethoxy)phenyl)propane,2,2-bis(4′-(1″-ethoxypropyloxy)phenyl)propane, tert-butyl4,4-bis(4′-(2″-tetrahydropyranyloxy)phenyl)valerate, tert-butyl4,4-bis(4′-(2″-tetrahydrofuranyloxy)phenyl)valerate, tert-butyl4,4-bis(4′-tert-butoxyphenyl)valerate, tert-butyl4,4-bis(4-tert-butoxycarbonyloxyphenyl)valerate, tert-butyl4,4-bis(4′-tert-butoxycarbonylmethyloxyphenyl)valerate, tert-butyl4,4-bis(4′-(1″-ethoxyethoxy)phenyl)valerate, tert-butyl4,4-bis(4′-(1″-ethoxypropyloxy)phenyl)valerate,tris(4-(2′-tetrahydropyranyloxy)phenyl)methane,tris(4-(2′-tetrahydrofuranyloxy)phenyl)methane,tris(4-tert-butoxyphenyl)methane,tris(4-tert-butoxycarbonyloxyphenyl)methane,tris(4-tert-butoxycarbonyloxymethylphenyl)methane,tris(4-(1′-ethoxyethoxy)phenyl)methane,tris(4-(1′-ethoxypropyloxy)phenyl)methane,1,1,2-tris(4′-(2″-tetrahydropyranyloxy)phenyl)ethane,1,1,2-tris(4′-(2″-tetrahydrofuranyloxy)phenyl)ethane,1,1,2-tris(4′-tert-butoxyphenyl)ethane,1,1,2-tris(4′-tert-butoxycarbonyloxyphenyl)ethane,1,1,2-tris(4′-tert-butoxycarbonylmethyloxyphenyl)ethane,1,1,2-tris(4′-(1′-ethoxyethoxy)phenyl)ethane, and1,1,2-tris(4′-(1′-ethoxypropyloxy)phenyl)ethane.

[0196] In the resist composition comprising the sulfonyldiazomethane offormula (1) or (1a) as the photoacid generator according to theinvention, an appropriate amount of the dissolution inhibitor is up to20 parts, and especially up to 15 parts by weight per 100 parts byweight of the solids in the resist composition. With more than 20 partsof the dissolution inhibitor, the resist composition becomes less heatresistant because of an increased content of monomer components.

[0197] Component (H)

[0198] In a chemical amplification, negative working, resist compositionas well, the sulfonyldiazomethane of formula (1) or (1a) according tothe invention may be used as the photoacid generator. This compositionfurther contains an alkali-soluble resin as component (H), examples ofwhich are intermediates of the above-described component (A) though notlimited thereto. Examples of the alkali-soluble resin includepoly(p-hydroxystyrene), poly(m-hydroxystyrene),poly(4-hydroxy-2-methylstyrene), poly(4-hydroxy-3-methylstyrene),poly(α-methyl-p-hydroxystyrene), partially hydrogenated p-hydroxystyrenecopolymers, p-hydroxystyrene-α-methyl-p-hydroxystyrene copolymers,p-hydroxystyrene-α-methylstyrene copolymers, p-hydroxystyrene-styrenecopolymers, p-hydroxystyrene-m-hydroxystyrene copolymers,p-hydroxystyrene-styrene copolymers, p-hydroxystyrene-acrylic acidcopolymers, p-hydroxystyrene-methacrylic acid copolymers,p-hydroxystyrene-methyl methacrylate copolymers,p-hydroxystyrene-acrylic acid-methyl methacrylate copolymers,p-hydroxystyrene-methyl acrylate copolymers,p-hydroxystyrene-methacrylic acid-methyl methacrylate copolymers,poly(methacrylic acid), poly(acrylic acid), acrylic acid-methyl acrylatecopolymers, methacrylic acid-methyl methacrylate copolymers, acrylicacid-maleimide copolymers, methacrylic acid-maleimide copolymers,p-hydroxystyrene-acrylic acid-maleimide copolymers, andp-hydroxystyrene-methacrylic acid-maleimide copolymers, but are notlimited to these combinations.

[0199] Preferred are poly(p-hydroxystyrene), partially hydrogenatedp-hydroxystyrene copolymers, p-hydroxystyrene-styrene copolymers,p-hydroxystyrene-acrylic acid copolymers, andp-hydroxystyrene-methacrylic acid copolymers.

[0200] Alkali-soluble resins comprising units of the following formula(2), (2′), (2″) or (2″′) are especially preferred.

[0201] Herein R⁴ is hydrogen or methyl; and R⁵ is a straight, branchedor cyclic alkyl group of 1 to 8 carbon atoms. The subscript x is 0 or apositive integer; y is a positive integer, satisfying x+y≦5, yy is 0 ora positive integer, satisfying x+yy≦5; M and N are positive integers,satisfying 0<N/(M+N)≦0.5; A and B are positive integers, C is 0 or apositive integer, satisfying 0<B/(A+B+C)≦0.5, ZZ is a divalent groupselected from among CH₂, CH(OH), CR⁵(OH), C═O and C(OR⁵)(OH), or atrivalent organic group represented by —C(OH)═; F is independently apositive integer, and H is a positive integer, satisfying0.001≦H/(H+F)≦0.1; and XX is 1 or 2.

[0202] The polymer should preferably have a weight average molecularweight (Mw) of 3,000 to 100,000. Many polymers with Mw of less than3,000 do not perform well and are poor in heat resistance and filmformation. Many polymers with Mw of more than 100,000 give rise to aproblem with respect to dissolution in the resist solvent and developer.The polymer should also preferably have a dispersity (Mw/Mn) of up to3.5, and more preferably up to 1.5. With a dispersity of more than 3.5,resolution is low in many cases. Although the preparation method is notcritical, a poly(p-hydroxystyrene) or similar polymer with a lowdispersity or narrow dispersion can be synthesized by living anionpolymerization.

[0203] To impart a certain function, suitable substituent groups may beintroduced into some of the phenolic hydroxyl and carboxyl groups on theforegoing polymer. Exemplary and preferred are substituent groups forimproving adhesion to the substrate, substituent groups for improvingetching resistance, and especially substituent groups which arerelatively stable against acid and alkali and effective for controllingsuch that the dissolution rate in an alkali developer of unexposed andlow exposed areas of a resist film may not become too high.Illustrative, non-limiting, substituent groups include 2-hydroxyethyl,2-hydroxypropyl, methoxymethyl, methoxycarbonyl, ethoxycarbonyl,methoxycarbonylmethyl, ethoxycarbonylmethyl, 4-methyl-2-oxo-4-oxoranyl,4-methyl-2-oxo-4-oxanyl, methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, acetyl, pivaloyl, adamantyl, isoboronyl, and cyclohexyl. Itis also possible to introduce acid-decomposable substituent groups suchas t-butoxycarbonyl and relatively acid-undecomposable substituentgroups such as t-butyl and t-butoxycarbonylmethyl.

[0204] In the resist composition, the above resin is blended in anydesired amount, preferably of 65 to 99 parts by weight, especially 70 to98 parts by weight per 100 parts by weight of the solids.

[0205] Also contained in the negative resist composition is (I) an acidcrosslinking agent capable of forming a crosslinked structure under theaction of an acid. Typical acid crosslinking agents are compounds havingat least two hydroxymethyl, alkoxymethyl, epoxy or vinyl ether groups ina molecule. Substituted glycoluril derivatives, urea derivatives, andhexa(methoxymethyl)melamine compounds are suitable as the acidcrosslinking agent in the chemically amplified, negative resistcomposition comprising the sulfonyldiazomethane. Examples includeN,N,N′,N′-tetramethoxymethylurea, hexamethoxymethylmelamine,tetraalkoxymethyl-substituted glycoluril compounds such astetrahydroxymethyl-substituted glycoluril andtetramethoxymethylglycoluril, and condensates of phenolic compounds suchas substituted or unsubstituted bis(hydroxymethylphenol) compounds andbisphenol A with epichlorohydrin. Especially preferred acid crosslinkingagents are 1,3,5,7-tetraalkoxymethylglycolurils such as1,3,5,7-tetramethoxymethylglycoluril,1,3,5,7-tetrahydroxymethylglycoluril, 2,6-dihydroxymethyl-p-cresol,2,6-dihydroxymethylphenol, 2,2′,6,6′-tetrahydroxymethyl-bisphenol A,1,4-bis[2-(2-hydroxypropyl)]benzene, N,N,N′,N′-tetramethoxymethylurea,and hexamethoxymethylmelamine.

[0206] An appropriate amount of the acid crosslinking agent is, but notlimited thereto, about 1 to 20 parts, and especially about 5 to 15 partsby weight per 100 parts by weight of the solids in the resistcomposition. The acid crosslinking agents may be used alone or inadmixture of any.

[0207] Component (J) is an alkali-soluble compound having a molecularweight of up to 2,500. Any suitable compound may be used although acompound having at least two phenol and/or carboxyl groups is preferred.Illustrative, non-limiting, examples of the alkali-soluble compound (J)include cresol, catechol, resorcinol, pyrogallol, phloroglucinol,bis(4-hydroxyphenyl)methane, 2,2-bis(4′-hydroxyphenyl)propane,bis(4-hydroxyphenyl)sulfone, 1,1,1-tris(4′-hydroxyphenyl)ethane,1,1,2-tris(4′-hydroxyphenyl)ethane, hydroxybenzophenone,4-hydroxyphenylacetic acid, 3-hydroxyphenylacetic acid,2-hydroxyphenylacetic acid, 3-(4-hydroxyphenyl)propionic acid,3-(2-hydroxyphenyl)propionic acid, 2,5-dihydroxyphenylacetic acid,3,4-dihydroxyphenylacetic acid, 1,2-phenylenediacetic acid,1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid,1,2-phenylenedioxydiacetic acid, 1,4-phenylenedipropanoic acid, benzoicacid, salicylic acid, 4,4-bis(4′-hydroxyphenyl)valeric acid,4-tert-butoxyphenylacetic acid, 4-(4-hydroxyphenyl)butyric acid,3,4-dihydroxymandelic acid, and 4-hydroxymandelic acid. Of these,salicylic acid and 4,4-bis(4′-hydroxyphenyl)valeric acid are preferred.They may be used alone or in admixture of two or more. Thealkali-soluble compound is blended in any desired amount, preferably of0 to 20 parts by weight, especially 2 to 10 parts by weight per 100parts by weight of the solids in the resist composition.

[0208] In the chemical amplification type resist composition accordingto the invention, there may be added such additives as a surfactant forimproving coating, and a light absorbing agent for reducing diffusereflection from the substrate.

[0209] Illustrative, non-limiting, examples of the surfactant includenonionic surfactants, for example, polyoxyethylene alkyl ethers such aspolyoxyethylene lauryl ether, polyoxyethylene stearyl ether,polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether,polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenolether and polyoxyethylene nonylphenol ether, polyoxyethylenepolyoxypropylene block copolymers, sorbitan fatty acid esters such assorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate,and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylenesorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitantrioleate, and polyoxyethylene sorbitan tristearate; fluorochemicalsurfactants such as EFTOP EF301, EF303 and EF352 (Tohkem Products K.K.),Megaface F171, F172 and F173 (Dai-Nippon Ink & Chemicals K.K.), FloradeFC430 and FC431 (Sumitomo 3M K.K.), Aashiguard AG710, Surflon S-381,S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfynol E1004, KH-10,KH-20, KH-30 and KH-40 (Asahi Glass K.K.); organosiloxane polymersKP341, X-70-092 and X-70-093 (Shin-Etsu Chemical Co., Ltd.), acrylicacid or methacrylic acid Polyflow No. 75 and No. 95 (Kyoeisha UshiKagaku Kogyo K.K.). Inter alia, FC430, Surflon S-381, Surfynol E1004,KH-20 and KH-30 are preferred. These surfactants may be used alone or inadmixture.

[0210] In the chemical amplification type resist composition accordingto the invention, the surfactant is preferably formulated in an amountof up to 2 parts, and especially up to 1 part by weight, per 100 partsby weight of the solids in the resist composition.

[0211] In the chemical amplification type resist composition accordingto the invention, a UV absorber may be added. Those UV absorbersdescribed in JP-A 11-190904 are useful, but the invention is not limitedthereto.

[0212] Exemplary UV absorbers are diaryl sulfoxide derivatives such asbis(4-hydroxyphenyl) sulfoxide, bis(4-tert-butoxyphenyl) sulfoxide,bis(4-tert-butoxycarbonyloxyphenyl) sulfoxide, andbis[4-(1-ethoxyethoxy)phenyl]sulfoxide; diarylsulfone derivatives suchas bis(4-hydroxyphenyl)sulfone, bis(4-tert-butoxyphenyl)sulfone,bis(4-tert-butoxycarbonyloxyphenyl)sulfone,bis[4-(1-ethoxyethoxy)-phenyl]sulfone, andbis[4-(1-ethoxypropoxy)phenyl]sulfone; diazo compounds such asbenzoquinonediazide, naphthoquinonediazide, anthraquinonediazide,diazofluorene, diazotetralone, and diazophenanthrone; quinonediazidegroup-containing compounds such as complete or partial ester compoundsbetween naphthoquinone-1,2-diazide-5-sulfonic acid chloride and2,3,4-trihydroxybenzophenone and complete or partial ester compoundsbetween naphthoquinone-1,2-diazide-4-sulfonic acid chloride and2,4,4′-trihydroxybenzophenone; tert-butyl 9-anthracenecarboxylate,tert-amyl 9-anthracenecarboxylate, tert-methoxymethyl9-anthracenecarboxylate, tert-ethoxyethyl 9-anthracenecarboxylate,2-tert-tetrahydropyranyl 9-anthracenecarboxylate, and2-tert-tetrahydrofuranyl 9-anthracenecarboxylate. The UV absorber may ormay not be added to the resist composition depending on the type ofresist composition. An appropriate amount of UV absorber, if added, is 0to 10 parts, more preferably 0.5 to 10 parts, most preferably 1 to 5parts by weight per 100 parts by weight of the base resin.

[0213] For the microfabrication of integrated circuits, any well-knownlithography may be used to form a resist pattern from the chemicalamplification type resist composition comprising thesulfonyldiazomethane photoacid generator of formula (1) or (1a) and theresin which changes solubility in an alkaline developer under the actionof acid according to the invention.

[0214] The composition is applied onto a substrate (e.g., Si, SiO₂, SiN,SiON, TiN, WSi, BPSG, SOG, organic anti-reflecting film, etc.) by asuitable coating technique such as spin coating, roll coating, flowcoating, dip coating, spray coating or doctor coating. The coating isprebaked on a hot plate at a temperature of 60 to 150° C. for about 1 to10 minutes, preferably 80 to 120° C. for 1 to 5 minutes. The resultingresist film is generally 0.1 to 2.0 μm thick. With a mask having adesired pattern placed above the resist film, the resist film is thenexposed to actinic radiation, preferably having an exposure wavelengthof up to 300 nm, such as UV, deep-UV, electron beams, x-rays, excimerlaser light, γ-rays and synchrotron radiation in an exposure dose ofabout 1 to 200 mJ/cm², preferably about 10 to 100 mJ/cm². The film isfurther baked on a hot plate at 60 to 150° C. for 1 to 5 minutes,preferably 80 to 120° C. for 1 to 3 minutes (post-exposure baking=PEB).

[0215] Thereafter the resist film is developed with a developer in theform of an aqueous base solution, for example, 0.1 to 5%, preferably 2to 3% aqueous solution of tetramethylammonium hydroxide (TMAH) for 0.1to 3 minutes, preferably 0.5 to 2 minutes by conventional techniquessuch as dipping, puddling or spraying. In this way, a desired resistpattern is formed on the substrate. It is appreciated that the resistcomposition of the invention is best suited for micro-patterning usingsuch actinic radiation as deep UV with a wavelength of 254 to 193 nm,vacuum UV with a wavelength of 157 nm, electron beams, x-rays, excimerlaser light, γ-rays and synchrotron radiation. With any of theabove-described parameters outside the above-described range, theprocess may sometimes fail to produce the desired pattern.

EXAMPLE

[0216] Examples of the invention are given below by way of illustrationand not by way of limitation.

Synthesis Example 1

[0217] Synthesis of 4-n-butoxythiophenol

[0218] In 200 g of ethanol were dissolved 86.5 g (0.5 mol) of4-bromophenol and 22 g (0.55 mol) of sodium hydroxide. To the solutionat 70° C., 75.4 g (0.55 mol) of n-butyl bromide was added dropwise. Thesolution was allowed to ripen for 4 hours and cooled to roomtemperature, after which 120 g of water was added. The oily matter wasseparated therefrom and concentrated by a rotary evaporator, yielding 90g of 4-n-butoxyphenyl bromide. This was used in the subsequent reactionwithout further purification.

[0219] Using 9.5 g (0.39 mol) of metallic magnesium, 300 g oftetrahydrofuran, and 90 g (0.39 mol) of the above 4-n-butoxyphenylbromide, a Grignard reagent was prepared in a conventional manner. TheGrignard reagent was ice cooled, to which 12.6 g (0.39 mol) of colloidalsulfur was added at a temperature below 20° C. The solution was ripenedfor 2 hours at room temperature, then ice cooled again. To the solution,60 g of conc. hydrochloric acid (12N) and 200 g of water were added. Theorganic layer thus separated was concentrated, obtaining 74 g (yield82%) of the end compound, 4-n-butoxythiophenol.

Synthesis Example 2

[0220] Synthesis of formaldehyde bis(4-n-butoxyphenylthio)acetal

[0221] In 180 g of ethanol were dissolved 45 g (0.25 mol) of the above4-n-butoxythiophenol and 10.3 g (0.26 mol) of sodium hydroxide. To thesolution, 15.9 g (0.19 mol) of dichloromethane was added dropwise at atemperature below 50° C. The solution was heated at 60° C. in an oilbath and ripened for 3 hours at the temperature. It was allowed to coolto room temperature, after which 300 g of water and 200 g ofdichloromethane were added. The organic layer was separated and thesolvent was removed therefrom by a rotary evaporator, collecting 46.1 g(yield 98%) of the end compound, formaldehydebis(4-n-butoxyphenylthio)acetal.

Synthesis Example 3

[0222] Synthesis of bis(4-n-butoxyphenylsulfonyl)methane

[0223] To 190 g of ethanol were added 46.1 g (0.122 mol) of theformaldehyde bis(4-n-butoxyphenylthio)acetal in Synthesis Example 2 and1.0 g (0.003 mol) of sodium tungstate. The solution was heated at 65° C.in an oil bath, to which 67 g (0.69 mol) of aqueous hydrogen peroxidewas added dropwise at a temperature below 70° C. The solution was keptat the temperature for 4 hours and then cooled in an ice bath whereuponwhite crystals precipitated. The crystals were filtered out, collecting43.2 g (yield 80%) of the end compound,bis(4-n-butoxyphenylsulfonyl)methane.

Synthesis Example 4

[0224] Synthesis of bis(4-n-butoxyphenylsulfonyl)diazomethane

[0225] In 200 g of dichloromethane were dissolved 22 g (0.05 mol) of thebis(4-n-butoxyphenylsulfonyl)methane in Synthesis Example 3 and 14.8 g(0.075 mol) of p-toluene-sulfonylazide. The solution was cooled in anice bath, 7.6 g (0.05 mol) of diazabicycloundecene (DBU) was added at atemperature below 5° C. The solution was ripened at the temperature for15 minutes, after which 100 g of water and 15 g of conc. hydrochloricacid (12N) were added. The organic layer was separated and washed with100 g of water, after which the solvent was removed by a rotaryevaporator, obtaining 37 g of an oily matter. It was purified by silicagel column chromatography (eluent: dichloromethane), obtaining 15 g(yield 64%) of the end compound,bis(4-n-butoxyphenylsulfonyl)diazomethane.

[0226] The thus obtained bis(4-n-butoxyphenylsulfonyl)diazomethane wasanalyzed by nuclear magnetic resonance (NMR) spectroscopy and infrared(IR) absorption spectroscopy, with the results shown below.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.964-1.013 triplet 6H (2) Hb 1.442-1.571multiplet 4H (3) Hc 1.754-1.847 multiplet 4H (4) Hd 4.021-4.064 triplet4H (5) He 6.970-7.000 doublet 4H (6) Hf 7.879-7.909 doublet 4H IR: cm⁻¹2954, 2953, 2117, 2100, 1593, 1497, 1470, 1344, 1309, 1263, 1225, 1207,1180, 1153, 1082, 1024, 981, 839, 806, 719, 688, 632, 582

Synthesis Example 5

[0227] Synthesis of 4-n-hexyloxythiophenol

[0228] In 200 g of ethanol were dissolved 86.5 g (0.5 mol) of4-bromophenol and 22 g (0.55 mol) of sodium hydroxide. To the solutionat 70° C., 90.8 g (0.55 mol) of n-hexyl bromide was added dropwise. Thesolution was allowed to ripen for 4 hours and cooled to roomtemperature, after which 120 g of water was added. The oily matter wasseparated therefrom and concentrated by a rotary evaporator, followed byvacuum distillation (boiling point 125-128° C./0.5 Torr), yielding 100 gof 4-n-hexyloxyphenyl bromide.

[0229] Using 9.0 g (0.39 mol) of metallic magnesium, 300 g oftetrahydrofuran, and 100 g (0.39 mol) of the above 4-n-hexyloxyphenylbromide, a Grignard reagent was prepared in a conventional manner. TheGrignard reagent was ice cooled, to which 12.6 g (0.39 mol) of colloidalsulfur was added at a temperature below 20° C. The solution was ripenedfor 2 hours at room temperature, then ice cooled again. To the solution,60 g of conc. hydrochloric acid (12N) and 200 g of water were added. Theorganic layer thus separated was concentrated, obtaining 83 g of an oilymatter. Vacuum distillation (boiling point 120-130° C./0.5 Torr) of theoily matter yielded 60 g (yield 57%) of the end compound,4-n-hexyloxythiophenol.

Synthesis Example 6

[0230] Synthesis of formaldehyde bis(4-n-hexyloxyphenylthio)acetal

[0231] In 240 g of ethanol were dissolved 60 g (0.285 mol) of the above4-n-hexyloxythiophenol and 12.0 g (0.30 mol) of sodium hydroxide. To thesolution, 18.1 g (0.214 mol) of dichloromethane was added dropwise at atemperature below 50° C. The solution was heated at 60° C. in an oilbath and ripened for 3 hours at the temperature. It was allowed to coolto room temperature, after which 300 g of water and 200 g ofdachloromethane ere added. The organic layer was separated and thesolvent was removed therefrom by a rotary evaporator, collecting 61.2 g(yield 99%) of the end compound, formaldehydebis(4-n-hexyloxyphenylthio)acetal.

Synthesis Example 7

[0232] Synthesis of bis(4-n-hexyloxyphenylsulfonyl)methane

[0233] To 240 g of ethanol were added 61.2 g (0.141 mol) of theformaldehyde bis(4-n-hexyloxyphenylthio)acetal in Synthesis Example 6and 1.0 g (0.003 mol) of sodium tungstate. The solution was heated at65° C. in an oil bath, to which 69 g (0.71 mol) of aqueous hydrogenperoxide was added dropwise at a temperature below 70° C. The solutionwas kept at the temperature for 4 hours and then cooled in an ice bathwhereupon white crystals precipitated. The crystals were filtered out,collecting 57 g (yield 81%) of the end compound,bis(4-n-hexyloxyphenylsulfonyl)methane.

Synthesis Example 8

[0234] Synthesis of bis(4-n-hexyloxyphenylsulfonyl)diazomethane

[0235] In 200 g of dichloromethane were dissolved 20 g (0.04 mol) of thebis(4-n-hexyloxyphenylsulfonyl)methane in Synthesis Example 7 and 11.9 g(0.06 mol) of p-toluene-sulfonylazide. The solution was cooled in an icebath, 6.1 g (0.04 mol) of diazabicycloundecene (DBU) was added at atemperature below 5° C. The solution was ripened at the temperature for15 minutes, after which 100 g of water and 10 g of conc. hydrochloricacid (12N) were added. The organic layer was separated and washed with100 g of water, after which the solvent was removed by a rotaryevaporator, obtaining 37 g of an oily matter. It was purified by silicagel column chromatography (eluent: dichloromethane), obtaining 14.8 g(yield 70%) of the end compound,bis(4-n-hexyloxyphenylsulfonyl)diazomethane.

[0236] The thus obtained bis(4-n-hexyloxyphenylsulfonyl)diazomethane wasanalyzed by NMR spectroscopy and IR spectroscopy, with the results shownbelow.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.891-0.938 triplet 6H (2) Hb 1.30-1.50multiplet 12H (3) Hc 1.766-1.859 quintuplet 4H (4) Hd 4.013-4.056triplet 4H (5) He 6.961-6.994 doublet 4H (6) Hf 7.881-7.904 doublet 4HIR: cm⁻¹ 2939, 2873, 2854, 2103, 1593, 1497, 1475, 1350, 1309, 1261,1213, 1180, 1151, 1084, 1022, 983, 831, 721, 690, 628, 580, 569

Synthesis Example 9

[0237] Synthesis of 4-n-hexyloxy-2-methylthiophenol

[0238] In 200 g of ethanol were dissolved 71.2 g (0.5 mol) of4-chloro-3-methylphenol and 22 g (0.55 mol) of sodium hydroxide. To thesolution at 70° C., 90.8 g (0.55 mol) of n-hexyl bromide was addeddropwise. The solution was allowed to ripen for 4 hours and cooled toroom temperature, after which 120 g of water was added. The oily matterwas separated therefrom and concentrated by a rotary evaporator,followed by vacuum distillation (boiling point 115-117° C./0.3 Torr),yielding 102 g of 4-n-hexyloxy-2-methylphenyl chloride.

[0239] Using 10.9 g (0.45 mol) of metallic magnesium, 150 g oftetrahydrofuran, and 102 g (0.45 mol) of the above4-n-hexyloxy-2-methylphenyl chloride, a Grignard reagent was prepared ina conventional manner. The Grignard reagent was ice cooled, to which14.3 g (0.45 mol) of colloidal sulfur was added at a temperature below20° C. The solution was ripened for 2 hours at room temperature, thenice cooled again. To the solution 60 g of conc. hydrochloric acid (12N)and 200 g of water were added. The organic layer thus separated wasconcentrated, obtaining 83 g of an oily matter. Vacuum distillation(boiling point 110-190° C./0.3 Torr) of the oily matter yielded 47 g(yield 42%) of the end compound, 4-n-hexyloxy-2-methylthiophenol.

Synthesis Example 10

[0240] Synthesis of formaldehydebis(4-n-hexyloxy-2-methylphenylthio)acetal

[0241] In 200 g of ethanol were dissolved 47 g (0.21 mol) of the above4-n-hexyloxy-2-methylthiophenol and 8.8 g (0.22 mol) of sodiumhydroxide. To the solution, 13.6 g (0.16 mol) of dichloromethane wasadded dropwise at a temperature below 50° C. The solution was heated at60° C. in an oil bath and ripened for 3 hours at the temperature. It wasallowed to cool to room temperature, after which 200 g of water and 150g of dichloromethane were added. The organic layer was separated and thesolvent was removed therefrom by a rotary evaporator, collecting 46.9 g(yield 97%) of the end compound, formaldehydebis(4-n-hexyloxy-2-methylphenylthio)acetal.

Synthesis Example 11

[0242] Synthesis of bis(4-n-hexyloxy-2-methylphenylsulfonyl)methane

[0243] To 200 g of ethanol were added 46.9 g (0.102 mol) of theformaldehyde bis(4-n-hexyloxy-2-methylphenylthio)acetal in SynthesisExample 10 and 1.0 g (0.003 mol) of sodium tungstate. The solution washeated at 65° C. in an oil bath, to which 53 g (0.55 mol) of aqueoushydrogen peroxide was added dropwise at a temperature below 70° C. Thesolution was kept at the temperature for 4 hours and then cooled in anice bath whereupon white crystals precipitated. The crystals werefiltered out, collecting 42.8 g (yield 80%) of the end compound,bis(4-n-hexyloxy-2-methylphenylsulfonyl)methane.

Synthesis Example 12

[0244] Synthesis of bis(4-n-hexyloxy-2-methylphenylsulfonyl)diazomethane

[0245] In 200 g of dichloromethane were dissolved 20 g (0.038 mol) ofthe bis(4-n-hexyloxy-2-methylphenylsulfonyl)methane in Synthesis Example11 and 11.3 g (0.057 mol) of p-toluenesulfonylazide. The solution wascooled in an ice bath, 5.8 g (0.038 mol) of diazabicycloundecene (DBU)was added at a temperature below 5° C. The solution was ripened at thetemperature for 15 minutes, after which 100 g of water and 10 g of conc.hydrochloric acid (12N) were added. The organic layer was separated andwashed with 100 g of water, after which the solvent was removed by arotary evaporator, obtaining 32 g of an oily matter. It was purified bysilica gel column chromatography (eluent: dichloromethane), obtaining11.1 g (yield 52%) of the end compound,bis(4-n-hexyloxy-2-methylphenylsulfonyl)diazomethane.

[0246] The thus obtainedbis(4-n-hexyloxy-2-methylphenylsulfonyl)diazomethane was analyzed by NMRspectroscopy and IR spectroscopy, with the results shown below.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.894-0.940 triplet 6H (2) Hb 1.33-1.50multiplet 12H (3) Hc 1.745-1.839 quintuplet 4H (4) Hd 3.967-4.010triplet 4H (5) He, Hg 6.722-6.747 multiplet 4H (6) Hf 7.776-7.808doublet 2H (7) Hh 2.533 singlet 6H IR: cm⁻¹ 2956, 2933, 2860, 2104,1604, 1566, 1473, 1346, 1298, 1254, 1227, 1169, 1142, 1065, 993, 970,864, 804, 715, 700, 675, 631, 596, 577, 532

Synthesis Example 13

[0247] Synthesis of 4-n-decyloxythiophenol

[0248] In 200 g of ethanol were dissolved 86.5 g (0.5 mol) of4-bromophenol and 22 g (0.55 mol) of sodium hydroxide. To the solutionat 70° C., 121.8 g (0.55 mol) of n-decyl bromide was added dropwise. Thesolution was allowed to ripen for 4 hours and cooled to roomtemperature, after which 120 g of water was added. The oily matter wasseparated therefrom and concentrated by a rotary evaporator, followed byvacuum distillation (boiling point 143-145° C./0.5 Torr), yielding 90 gof 4-n-decyloxyphenyl bromide.

[0249] Using 10.9 g (0.447 mol) of metallic magnesium, 335 g oftetrahydrofuran, and 140 g (0.447 mol) of the above 4-n-decyloxyphenylbromide, a Grignard reagent was prepared in a conventional manner. TheGrignard reagent was ice cooled, to which 14.3 g (0.447 mol) ofcolloidal sulfur was added at a temperature below 20° C. The solutionwas ripened for 2 hours at room temperature, then ice cooled again. Tothe solution, 30 g of conc. hydrochloric acid (12N) and 150 g of waterwere added. The organic layer thus separated was concentrated, obtaining77 g of an oily matter. Vacuum distillation (boiling point 145-149°C./0.4 Torr) of the oily matter yielded 54 g (yield 40%) of the endcompound, 4-n-decyloxythiophenol.

Synthesis Example 14

[0250] Synthesis of formaldehyde bis(4-n-decyloxyphenylthio)acetal

[0251] In 200 g of ethanol were dissolved 54 g (0.203 mol) of the above4-n-decyloxythiophenol and 8.5 g (0.21 mol) of sodium hydroxide. To thesolution, 12.9 g (0.15 mol) of dichloromethane was added dropwise at atemperature below 50° C. The solution was heated at 60° C. in an oilbath and ripened for 3 hours at the temperature. It was allowed to coolto room temperature, after which 100 g of water and 150 g ofdichloromethane were added. The organic layer was separated and thesolvent was removed therefrom by a rotary evaporator, collecting 55 g(yield 100%) of the end compound, formaldehydebis(4-n-decyloxyphenylthio)acetal.

Synthesis Example 15

[0252] Synthesis of bis(4-n-decyloxyphenylsulfonyl)methane

[0253] To 220 g of ethanol were added 55 g (0.101 mol) of theformaldehyde bis(4-n-decyloxyphenylthio)acetal in Synthesis Example 14and 1.0 g (0.003 mol) of sodium tungstate. The solution was heated at65° C. in an oil bath, to which 53 g (0.55 mol) of aqueous hydrogenperoxide was added dropwise at a temperature below 70° C. The solutionwas kept at the temperature for 4 hours and then cooled in an ice bathwhereupon white crystals precipitated. The crystals were filtered out,collecting 52 g (yield 85%) of the end compound,bis(4-n-decyloxyphenylsulfonyl)methane.

Synthesis Example 16

[0254] Synthesis of bis(4-n-decyloxyphenylsulfonyl)diazomethane

[0255] In 100 g of dichloromethane were dissolved 10 g (0.016 mol) ofthe bis(4-n-decyloxyphenylsulfonyl)methane in Synthesis Example 15 and3.9 g (0.02 mol) of p-toluene-sulfonylazide. The solution was cooled inan ice bath, 2.4 g (0.016 mol) of diazabicycloundecene (DBU) was addedat a temperature below 5° C. The solution was ripened at the temperaturefor 15 minutes, after which 50 g of water and 5 g of conc. hydrochloricacid (12N) were added. The organic layer was separated and washed with100 g of water, after which the solvent was removed by a rotaryevaporator, obtaining 14 g of an oily matter. This was purified bysilica gel column chromatography (eluent: dichloromethane), obtaining7.0 g (yield 69%) of the end compound,bis(4-n-decyloxyphenylsulfonyl)diazomethane.

[0256] The thus obtained bis(4-n-decyloxyphenylsulfonyl)diazomethane wasanalyzed by NMR spectroscopy and IR spectroscopy, with the results shownbelow.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.861-0.906 triplet 6H (2) Hb 1.20-1.50multiplet 28H (3) Hc 1.767-1.859 quintuplet 4H (4) Hd 4.011-4.055triplet 4H (5) He 6.970-7.000 doublet 4H (6) Hf 7.881-7.911 doublet 4HIR: cm⁻¹ 2920, 2852, 2106, 1593, 1497, 1475, 1350, 1311, 1263, 1213,1178, 1153, 1115, 1084, 1014, 982, 833, 719, 687, 629, 580

Synthesis Example 17

[0257] Synthesis of 4-n-decyloxythiophenol

[0258] In 200 g of ethanol were dissolved 86.5 g (0.5 mol) of4-bromophenol and 22 g (0.55 mol) of sodium hydroxide. To the solutionat 70° C., 137 g (0.55 mol) of n-dodecyl bromide was added dropwise. Thesolution was allowed to ripen for 4 hours and cooled to roomtemperature, after which 120 g of water was added. The oily matterseparated therefrom was concentrated by a rotary evaporator, followed byvacuum distillation (boiling point 178-180° C./0.5 Torr), yielding 110 gof 4-n-dodecyloxyphenyl bromide.

[0259] Using 7.8 g (0.322 mol) of metallic magnesium, 240 g oftetrahydrofuran, and 110 g (0.322 mol) of the above 4-n-dodecyloxyphenylbromide, a Grignard reagent was prepared in a conventional manner. TheGrignard reagent was ice cooled, to which 7.82 g (0.322 mol) ofcolloidal sulfur was added at a temperature below 20° C. The solutionwas ripened for 2 hours at room temperature, then ice cooled again. Tothe solution, 20 g of conc. hydrochloric acid (12N) and 100 g of waterwere added. The organic layer thus separated was concentrated, obtaining100 g of an oily matter. Vacuum distillation (boiling point 185-190°C./0.4 Torr) of the oily matter yielded 33 g (yield 35%) of the endcompound, 4-n-dodecyloxythiophenol.

Synthesis Example 18

[0260] Synthesis of formaldehyde bis(4-n-dodecyloxyphenylthio)acetal

[0261] In 165 g of ethanol were dissolved 33 g (0.112 mol) of the above4-n-dodecyloxythiophenol and 4.8 g (0.12 mol) of sodium hydroxide. Tothe solution, 7.6 g (0.089 mol) of dichloromethane was added dropwise ata temperature below 50° C. The solution was heated at 60° C. in an oilbath and ripened for 3 hours at the temperature. It was allowed to coolto room temperature, after which 100 g of water and 100 g ofdichloromethane were added. The organic layer was separated and thesolvent was removed therefrom by a rotary evaporator, collecting 30 g(yield 89%) of the end compound, formaldehydebis(4-n-dodecyloxyphenylthio)acetal.

Synthesis Example 19

[0262] Synthesis of bis(4-n-dodecyloxyphenylsulfonyl)methane

[0263] To 150 g of ethanol were added 30 g (0.05 mol) of theformaldehyde bis(4-n-dodecyloxyphenylthio)acetal in Synthesis Example 18and 0.3 g (0.001 mol) of sodium tungstate. The solution was heated at65° C. in an oil bath, to which 24 g (0.25 mol) of aqueous hydrogenperoxide was added dropwise at a temperature below 70° C. The solutionwas kept at the temperature for 4 hours and then cooled in an ice bathwhereupon white crystals precipitated. The crystals were filtered out,collecting 31 g (yield 93%) of the end compound,bis(4-n-dodecyloxyphenylsulfonyl)methane.

Synthesis Example 20

[0264] Synthesis of bis(4-n-dodecyloxyphenylsulfonyl)diazomethane

[0265] In 100 g of dichloromethane were dissolved 15 g (0.022 mol) ofthe bis(4-n-dodecyloxyphenylsulfonyl)methane in Synthesis Example 19 and5.9 g (0.03 mol) of p-toluene-sulfonylazide. The solution was cooled inan ice bath, 3.4 g (0.022 mol) of diazabicycloundecene (DBU) was addedat a temperature below 5° C. The solution was ripened at the temperaturefor 15 minutes, after which 100 g of water and 8 g of conc. hydrochloricacid (12N) were added. The organic layer was separated and washed with100 g of water, after which the solvent was removed by a rotaryevaporator, obtaining 20 g of an oily matter. It was purified by silicagel column chromatography (eluent: dichloromethane), obtaining 11 g(yield 70%) of the end compound,bis(4-n-dodecyloxyphenylsulfonyl)diazomethane.

[0266] The thus obtained bis(4-n-dodecyloxyphenylsulfonyl)diazomethanewas analyzed by NMR spectroscopy and IR spectroscopy, with the resultsshown below.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.868-0.903 triplet 6H (2) Hb 1.20-1.50multiplet 36H (3) Hc 1.767-1.859 quintuplet 4H (4) Hd 4.012-4.055triplet 4H (5) He 6.970-7.000 doublet 4H (6) Hf 7.881-7.911 doublet 4HIR: cm⁻¹ 2920, 2850, 2116, 1593, 1497, 1471, 1348, 1329, 1306, 1267,1221, 1159, 1080, 997, 976, 835, 721, 690, 633, 580, 563

Synthesis Example 21

[0267] Synthesis of bis(4-n-octyloxyphenylsulfonyl)diazomethane

[0268] The end product, bis(4-n-octyloxyphenylsulfonyl)diazomethane, wassynthesized as in Synthesis Examples 5 to 8 except that n-octyl bromidewas used instead of the n-hexyl bromide in Synthesis Example 5.

[0269] The thus obtained bis(4-n-octyloxyphenylsulfonyl)diazomethane wasanalyzed by NMR spectroscopy and IR spectroscopy, with the results shownbelow.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.869-0.914 triplet 6H (2) Hb 1.30-1.49multiplet 20H (3) Hc 1.767-1.860 quintuplet 4H (4) Hd 4.012-4.055triplet 4H (5) He 6.970-7.000 doublet 4H (6) Hf 7.881-7.910 doublet 4HIR: cm⁻¹ 2922, 2856, 2104, 1593, 1574, 1498, 1473, 1398, 1356, 1340,1308, 1267, 1227, 1149, 1080, 1030, 999, 976, 839, 719, 690, 625, 579,565

Synthesis Example 22

[0270] Synthesis of bis(4-n-octylphenylsulfonyl)diazomethane

[0271] The end product, bis(4-n-octylphenylsulfonyl)diazomethane, wassynthesized as in Synthesis Examples 5 to 8 except that commerciallyavailable 1-bromo-4-octylbenzene (Tokyo Chemical Industry Co., Ltd.) wasused instead of the 4-n-hexyloxyphenyl bromide obtained as theintermediate in Synthesis Example 5.

[0272] The thus obtained bis(4-n-octylphenylsulfonyl)diazomethane wasanalyzed by NMR spectroscopy and IR spectroscopy, with the results shownbelow.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.863-0.908 triplet 6H (2) Hb 1.20-1.40multiplet 20H (3) Hc 1.596-1.694 quintuplet 4H (4) Hd 2.673-2.734triplet 4H (5) He 7.344-7.373 doublet 4H (6) Hf 7.874-7.903 doublet 4HIR: cm⁻¹ 2924, 2856, 2104, 1595, 1470, 1406, 1358, 1344, 1319, 1217,1157, 1120, 1082, 978, 843, 698, 677, 623, 582, 569, 530

Synthesis Example 23

[0273] Synthesis ofbis(3,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane

[0274] The end product,bis(3,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane, wassynthesized as in Synthesis Examples 5 to 8 except that2,6-dimethyl-4-bromophenol was used instead of the bromophenol inSynthesis Example 5.

[0275] The thus obtainedbis(3,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane was analyzed byNMR spectroscopy and IR spectroscopy, with the results shown below.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.898-0.945 triplet 6H (2) Hb 1.30-1.56multiplet 12H (3) Hc 1.770-1.864 multiplet 4H (4) Hd 3.788-3.831 triplet4H (5) He 2.321 singlet 12H (6) Hf 7.594 singlet 4H IR: cm⁻¹ 2954, 2929,2856, 2117, 1470, 1379, 1342, 1281, 1215, 1151, 1101, 980, 930, 897,708, 669, 613, 534

Synthesis Example 24

[0276] Synthesis of 4-bromo-2,5-dimethyl-n-hexyloxybenzene

[0277] In 250 g of ethanol were dissolved 250 g (2.05 mol) of2,5-dimethylphenol (or p-xylenol), 90 g (2.25 mol) of sodium hydroxideand 371 g (2.25 mol) of n-hexyl bromide. The solution was heated for 2hours in an oil bath at 80° C. Water, 500 g, was added to the reactionmixture, from which an oily matter was separated. Vacuum distillation ofthe oily matter yielded 384 g of 2,5-dimethyl-1-n-hexyloxy-benzene.Next, 129 g (0.625 mol) of 2,5-dimethyl-1-n-hexyloxybenzene wasdissolved in 625 g of 1,2-dichloroethane. To the solution kept in an icebath, 100 g (0.625 mol) of bromine was added dropwise at a temperaturebelow 5C. At the end of dropwise addition, 500 g of water was added. Theorganic layer was separated therefrom and washed with 300 g of anaqueous solution of 5 wt % sodium hydrogen carbonate. The organic layerwas concentrated to remove the solvent, leaving an oily matter. Vacuumdistillation (boiling point 114-124° C./0.5 Torr) of the oily matteryielded 174 g of 4-bromo-2,5-dimethyl-n-hexyloxybenzene.

[0278] At the end of distillation, the product,4-bromo-2,5-dimethyl-n-hexyloxybenzene crystallized.

Synthesis Example 25

[0279] Synthesis of 2,5-dimethyl-4-n-hexyloxythiophenol

[0280] Using 14.8 g (0.61 mol) of metallic magnesium, 426 g oftetrahydrofuran, and 174 g (0.61 mol) of the4-bromo-2,5-dimethyl-n-hexyloxybenzene obtained in Synthesis Example 24,a Grignard reagent was prepared in a conventional manner. In an icebath, 18.5 g (0.578 mol) of colloidal sulfur was added to the Grignardreagent at a temperature below 20° C. The solution was ripened for 2hours at room temperature, then ice cooled again. To the solution, 90 gof conc. hydrochloric acid (12N) and 300 g of water were added. Theorganic layer was separated and concentrated, obtaining 145 g of an oilymatter. Vacuum distillation (boiling point 131-134° C./0.5 Torr) of theoily matter yielded 75 g of the end compound,2,5-dimethyl-4-n-hexyloxythiophenol.

Synthesis Example 26

[0281] Synthesis ofbis(2,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane

[0282] The end product,bis(2,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane was synthesizedas in Synthesis Examples 5 to 8 except that2,5-dimethyl-4-n-hexyloxythiophenol in Synthesis Example 25 was usedinstead of the 4-n-hexyloxythiophenol in Synthesis Example 6.

[0283] The thus obtainedbis(2,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane was analyzed byNMR spectroscopy and IR spectroscopy, with the results shown below.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.896-0.943 triplet 6H (2) Hb 1.30-1.42multiplet 8H (3) Hc 1.43-1.53 multiplet 4H (4) Hd 1.76-1.86 multiplet 4H(5) He 3.93-3.97 triplet 4H (6) Hf 2.12 singlet 6H (7) Hg 2.48 singlet6H (8) Hi 6.51 singlet 2H (9) Hj 7.49 singlet 2H IR: cm⁻¹ 2956, 2935,2858, 2102, 1602, 1562, 1502, 1465, 1392, 1375, 1340, 1327, 1263, 1232,1143, 1136, 1045, 1036, 964, 677, 613, 580, 562, 540

Synthesis Example 27

[0284] Synthesis ofbis(4-n-hexyloxy-2,3,5-trimethylphenylsulfonyl)diazomethane

[0285] The end product,bis(4-n-hexyloxy-2,3,5-trimethyl-phenylsulfonyl)diazomethane wassynthesized as in Synthesis Examples 24 to 26 except that2,3,6-trimethylphenol was used instead of the 2,5-dimethylphenol inSynthesis Example 24.

[0286] The thus obtainedbis(4-n-hexyloxy-2,3,5-trimethyl-phenylsulfonyl)diazomethane wasanalyzed by NMR spectroscopy and IR spectroscopy, with the results shownbelow.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.90-0.95 triplet 6H (2) Hb 1.33-1.40multiplet 8H (3) Hc 1.45-1.54 multiplet 4H (4) Hd 1.75-1.84 multiplet 4H(5) He 3.67-3.71 triplet 4H (6) Hf 2.11 singlet 6H (7) Hg 2.21 singlet6H (8) Hi 2.34 singlet 6H (9) Hj 7.50 singlet 2H IR: cm⁻¹ 2957, 2927,2860, 2098, 1465, 1377, 1344, 1329, 1277, 1228, 1211, 1149, 1139, 1093,669, 636, 607, 580, 569, 548

Synthesis Example 28

[0287] Synthesis ofbis(2-methyl-4-n-hexyloxy-5-isopropylphenylsulfonyl)diazomethane

[0288] The end product,bis(2-methyl-4-n-hexyloxy-5-isopropylphenylsulfonyl)diazomethane wassynthesized as in Synthesis Examples 24 to 26 except thatthymol(2-isopropyl-5-methylphenol) was used instead of the2,5-dimethylphenol in Synthesis Example 24.

[0289] The thus obtainedbis(2-methyl-4-n-hexyloxy-5-isopropylphenylsulfonyl)diazomethane wasanalyzed by NMR spectroscopy and IR spectroscopy, with the results shownbelow.

¹H-NMR: CDCl₃ (ppm) (1) Ha 0.90-0.94 triplet 6H (2) Hb 1.32-1.40multiplet 8H (3) Hc 1.44-1.54 multiplet 4H (4) Hd 1.78-1.87 multiplet 4H(5) He 3.99-4.03 triplet 4H (6) Hf 1.215-1.238 doublet 12H (7) Hg3.19-3.33 multiplet 2H (8) Hi 6.67 singlet 2H (9) Hj 2.56 singlet 6H(10) Hh 7.75 singlet 2H IR: cm⁻¹ 2958, 2933, 2866, 2110, 1601, 1558,1500, 1469, 1456, 1390, 1363, 1350, 1336, 1325, 1282, 1255, 1144, 1122,1076, 1041, 1030, 1012, 968, 902, 733, 677, 652, 596, 579, 548, 517

Examples 1-24 and Comparative Examples 1-3

[0290] Resist materials were formulated in accordance with theformulation shown in Tables 1-to 3. The components used are shown below.

[0291] Polymer A: poly(p-hydroxystyrene) in which hydroxyl groups areprotected with 15 mol % of 1-ethoxyethyl groups and 15 mol % oftert-butoxycarbonyl groups, having a weight average molecular weight of12,000.

[0292] Polymer B: poly(p-hydroxystyrene) in which hydroxyl groups areprotected with 30 mol % of 1-ethoxyethyl groups, having a weight averagemolecular weight of 12,000.

[0293] Polymer C: poly(p-hydroxystyrene) in which hydroxyl groups areprotected with 15 mol % of 1-ethoxyethyl groups and 10 mol % oftert-butoxycarbonyl groups, having a weight average molecular weight of11,000.

[0294] Polymer D: poly(p-hydroxystyrene) in which hydroxyl groups areprotected with 25 mol % of 1-ethoxyethyl groups and crosslinked with 3mol % of 1,2-propanediol divinyl ether, having a weight averagemolecular weight of 13,000.

[0295] Polymer E: poly(p-hydroxystyrene) in which hydroxyl groups areprotected with 25 mol % of tert-butoxycarbonyl groups, having a weightaverage molecular weight of 12,000.

[0296] Polymer F: p-hydroxystyrene/2-ethyl-2-adamantyl acrylatecopolymer having a compositional ratio (molar ratio) of 70:30 and aweight average molecular weight of 15,000.

[0297] Polymer G: p-hydroxystyrene/1-ethyl-1-norbornene methacrylatecopolymer having a compositional ratio (molar ratio) of 70:30 and aweight average molecular weight of 15,000.

[0298] Polymer H: p-hydroxystyrene/tert-butyl acrylate copolymer havinga compositional ratio (molar ratio) of 65:35 and a weight averagemolecular weight of 15,000.

[0299] Polymer I: p-hydroxystyrene/1-ethylcyclopentyl methacrylatecopolymer having a compositional ratio (molar ratio) of 65:35 and aweight average molecular weight of 15,000.

[0300] Polymer J: p-hydroxystyrene/1-ethylcyclopentylmethacrylate/styrene copolymer having a compositional ratio (molarratio) of 65:10:25 and a weight average molecular weight of 12,000.

[0301] Polymer K: p-hydroxystyrene/indene copolymer having acompositional ratio (molar ratio) of 80:20 in which hydroxyl groups onhydroxystyrene are protected with 20 mol % of tert-butoxycarbonylgroups, having a weight average molecular weight of 10,000.

[0302] Polymer L: p-hydroxystyrene/indene/1-ethyl-1-norbornenemethacrylate copolymer having a compositional ratio (molar ratio) of70:10:20 and a weight average molecular weight of 10,000.

[0303] Polymer M: p-hydroxystyrene/indene/1-ethyl-1-norbornenemethacrylate copolymer having a compositional ratio (molar ratio) of70:15:15 and a weight average molecular weight of 10,000.

[0304] Polymer N: poly(p-hydroxystyrene) in which hydroxyl groups areprotected with 8 mol % of acetyl groups, having a weight averagemolecular weight of 8,000.

[0305] PAG1: bis(4-n-hexyloxy-2-methylphenylsulfonyl)diazomethane

[0306] PAG2: bis(4-n-octylphenylsulfonyl)diazomethane

[0307] PAG3: bis(3,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane

[0308] PAG4: bis(2,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane

[0309] PAG5: (4-tert-butoxyphenyl)diphenylsulfonium 10-camphorsulfonate

[0310] PAG6: bis(4-methoxyphenylsulfonyl)diazomethane

[0311] PAG7: bis(cyclohexylsulfonyl)diazomethane

[0312] PAG8: bis(2,4-dimethylphenylsulfonyl)diazomethane

[0313] PAG9: N-10-camphorsulfonyloxysuccinimide

[0314] Crosslinker A: 1,3,5,7-tetramethoxymethylglycoluril

[0315] Dissolution inhibitor:bis(4-(2′-tetrahydropyranyloxy)phenyl)methane

[0316] Basic compound A: tri-n-butylamine

[0317] Basic compound B: tris(2-methoxyethyl)amine

[0318] Organic acid derivative A: 4,4-bis(4′-hydroxyphenyl)valeric acid

[0319] Organic acid derivative B: salicylic acid

[0320] Surfactant A: FC-430 (Sumitomo 3M K.K.)

[0321] Surfactant B: Surflon S-381 (Asahi Glass K.K.)

[0322] UV absorber: 9,10-dimethylanthracene

[0323] Solvent A: propylene glycol methyl ether acetate

[0324] Solvent B: ethyl lactate

[0325] The resist materials thus obtained were each filtered through a0.2-μm Teflon filter, thereby giving resist solutions. These resistsolutions were spin-coated onto silicon wafers having an organicantireflection film (Brewer Science, DUV-44) of 800 Å thick coatedthereon, so as to give a dry thickness of 0.6 μm.

[0326] The coated wafer was then baked on a hot plate at 100° C. for 90seconds. The resist films were exposed to ⅔ annular illumination usingan excimer laser stepper NSR-S202A (Nikon K.K., NA 0.6), then baked(PEB) at 110° C. for 90 seconds, and developed with a solution of 2.38%tetramethylammonium hydroxide in water, thereby giving positive patterns(Examples 1 to 23 and Comparative Examples 1-3) or negative pattern(Example 24).

[0327] The resulting resist patterns were evaluated as described below.

[0328] Resist Pattern Evaluation

[0329] The optimum exposure dose (sensitivity Eop) was the exposure dosewhich provided a 1:1 resolution at the top and bottom of a 0.18-μmline-and-space pattern. The minimum line width (μm) of a line-and-spacepattern which was ascertained separate at this dose was the resolutionof a test resist. The shape in cross section of the resolved resistpattern was examined under a scanning electron microscope. The depth offocus (DOF) was determined by offsetting the focal point and judging theresist to be satisfactory when the resist pattern shape was keptrectangular and the resist pattern film thickness was kept above 80% ofthat at accurate focusing.

[0330] The PED stability of a resist was evaluated by effectingpost-exposure bake (PED) after 24 hours of holding from exposure at theoptimum dose and determining a variation in line width (or groove widthfor the negative resist). The less the variation, the greater is the PEDstability.

[0331] The results of resist pattern evaluation are shown in Table 4.

[0332] Other Evaluation

[0333] The solubility of resist material in a solvent mixture wasexamined by visual observation and in terms of clogging upon filtration.

[0334] With respect to the applicability of a resist solution, unevencoating was visually observed. Additionally, using a film gage CleanTrack Mark 8 (Dai-Nippon Screen Manufacturing Co., Ltd., LightInterference Thickness Measuring Apparatus Ramda Ace VM-3010), thethickness of a resist film on a common wafer was measured at differentpositions, based on which a variation from the desired coating thickness(0.6 μm) was calculated. The applicability was rated “good” when thevariation was within 0.5% (that is, within 0.003 μm), “unacceptable”when the variation was within 1%, and “poor” when the variation was morethan 1%.

[0335] Storage stability was judged in terms of foreign matterprecipitation or sensitivity change with the passage of time. After theresist solution was aged for 100 days at the longest, the number ofparticles of greater than 0.3 μm per ml of the resist solution wascounted by means of a particle counter KL-20A (Rion K.K.), and theforeign matter precipitation was determined “good” when the number ofparticles is not more than 5. Also, the sensitivity change was rated“good” when a change with time of sensitivity (Eop) was within 5% fromthat immediately after preparation, and “poor” when the change is morethan 5%.

[0336] Debris appearing on the developed pattern was observed under ascanning electron microscope (TDSEM) model S-7280H (Hitachi, Ltd.). Theresist film was rated “good” when the number of foreign particles was upto 10 per 100 μm², “unacceptable” when from 11 to 15, and “poor” whenmore than 15.

[0337] Debris left after resist peeling was examined using a surfacescanner Surf-Scan 6220 (Tencol Instruments). A resist-coated 8-inchwafer was subjected to entire exposure rather than patterned exposure,processed in a conventional manner, and developed with a 2.38% TMAHsolution before the resist film was peeled off (only the resist film inthe exposed area was peeled). After the resist film was peeled, thewafer was examined and rated “good” when the number of foreign particlesof greater than 0.20 μm was up to 100, “unacceptable” when from 101 to150, and “poor” when more than 150.

[0338] The results are shown in Table 5. TABLE 2 Composition Example(pbw) 1 2 3 4 5 6 7 8 9 10 11 12 Polymer A 80 40 Polymer B 80 Polymer C80 Polymer D 80 Polymer E 80 Polymer F 80 Polymer G 80 Polymer H 80Polymer I 80 Polymer J 80 Polymer K 80 Polymer L 80 Polymer M Polymer NPAG1 2 2 1 PAG2 2 1 2 2 PAG3 2 2 2 PAG4 2 2 2 PAG5 1 1 2 PAG6 1 PAG7 1PAG8 1 PAG9 1 1 Dissolution inhibitor Basic compound A 0.3 0.3 0.2 0.30.3 0.3 0.3 0.3 Basic compound B 0.2 0.3 0.3 0.3 0.3 Organic acid 0.50.5 0.5 derivative A Organic acid 0.5 derivative B Surfactant A 0.3 0.30.3 0.3 0.3 0.3 Surfactant B 0.3 0.3 0.3 0.3 0.3 0.3 UV absorber SolventA 385 385 385 385 280 382 385 385 385 385 280 385 Solvent B 105 105

[0339] TABLE 2 Composition Example (pbw) 13 14 15 16 17 18 19 20 21 2223 24 Polymer A 40 60 Polymer B 60 75 Polymer C 40 40 Polymer D 70 40 6040 Polymer E 40 10 Polymer F Polymer G 40 Polymer H Polymer I 10 20Polymer J Polymer K 40 Polymer L 40 20 70 Polymer M 40 20 Polymer N 80PAG1 2 2 2 PAG2 2 2 2 PAG3 2 2 1 2 2 PAG4 2 2 2 2 PAG5 2 1 1 1 PAG6 2 2PAG7 1 1.5 1.5 1 PAG8 0.5 PAG9 1 1 1 Crosslinker A 20 Dissolution 5inhibitor Basic compound A 0.2 0.3 0.3 0.3 Basic compound B 0.3 0.3 0.30.3 0.2 0.3 0.3 0.3 0.3 Organic acid 0.5 0.5 derivative A Organic acid0.3 derivative B Surfactant A 0.3 0.3 0.3 0.3 0.3 0.3 Surfactant B 0.30.3 0.3 0.3 0.3 UV absorber 0.5 Solvent A 385 385 280 280 385 385 385280 385 385 280 385 Solvent B 105 105 105 105

[0340] TABLE 3 Composition Comparative Example (pbw) 1 2 3 Polymer A 8040 Polymer E 80 Polymer K 40 PAG5 PAG6 2.5 PAG7 1 PAG8 2.5 2.5 PAG9 1Dissolution inhibitor Basic compound A 0.125 Basic compound B 0.1250.125 Organic acid derivative A 0.5 Organic acid derivative B SurfactantA 0.25 0.25 Surfactant B 0 0.25 UV absorber Solvent A 385 385 385Solvent B

[0341] TABLE 4 24 hr PED DOF at dimensional Sensitivity Resolution 0.18μm Off-focus stability (mJ/cm²) (μm) Profile (μm) profile** (nm) Example1 31 0.14 rectangular 1.1 rectangular −8 Example 2 27 0.14 rectangular1.1 rectangular −10 Example 3 29 0.14 rectangular 1.0 rectangular −9Example 4 28 0.14 rectangular 1.1 rectangular −10 Example 5 35 0.16rectangular 1.0 rectangular 10 Example 6 33 0.15 rectangular 1.1rectangular −8 Example 7 32 0.14 rectangular 1.1 rectangular −10 Example8 35 0.16 rectangular 1.0 rectangular −8 Example 9 32 0.14 rectangular1.1 rectangular −10 Example 10 34 0.15 rectangular 1.0 rectangular −8Example 11 37 0.16 rectangular 0.8 rectangular 8 Example 12 33 0.15rectangular 1.0 rectangular −10 Example 13 32 0.15 rectangular 1.0rectangular −8 Example 14 28 0.14 rectangular 1.0 rectangular −10Example 15 30 0.14 rectangular 1.1 rectangular −8 Example 16 29 0.15rectangular 1.0 rectangular −8 Example 17 32 0.14 rectangular 1.0rectangular −10 Example 18 30 0.14 rectangular 1.0 rectangular −8Example 19 35 0.15 rectangular 1.0 rectangular −8 Example 20 28 0.14rectangular 1.1 rectangular −10 Example 21 32 0.15 rectangular 1.0rectangular −10 Example 22 35 0.14 rectangular 1.1 rectangular −10Example 23 28 0.14 rectangular 1.1 rectangular −8 Example 24 40 0.16rectangular 0.8 rectangular −8 Comparative 25 0.15 forward taper 0.8forward taper −10 Example 1 Comparative 32 0.15 rounded head 0.8 roundedhead −8 Example 2 Comparative 35 0.15 forward taper 0.8 forward taper−10 Example 3

[0342] TABLE 5 Debris Foreign 100 day after particles Dis- Applica-storage develop- after solution tion stability ment peeling Example 1good good good good good Example 2 good good good good good Example 3good good good good good Example 4 good good good good good Example 5good good good good good Example 6 good good good good good Example 7good good good good good Example 8 good good good good good Example 9good good good good good Example 10 good good good good good Example 11good good good good good Example 12 good good good good good Example 13good good good good good Example 14 good good good good good Example 15good good good good good Example 16 good good good good good Example 17good good good good good Example 18 good good good good good Example 19good good good good good Example 20 good good good good good Example 21good good good good good Example 22 good good good good good Example 23good good good good good Example 24 good good good good good Com- goodgood <30 days poor unaccept- parative (sensi- able Example 1 tivitychanged) Com- good good good unaccept- poor parative able Example 2 Com-good good good poor poor parative Example 3

Examples 25-30 and Comparative Examples 4-8

[0343] Resist solutions having formulations shown in Table 6 wereprepared. The components in Table 6 other than the components describedabove were as follows.

[0344] PAG10: bis(4-ethyloxyphenylsulfonyl)diazomethane

[0345] PAG11: bis(4-n-propyloxyphenylsulfonyl)diazomethane

[0346] PAG12: bis(4-tert-butylphenylsulfonyl)diazomethane

[0347] PAG13: bis(4-cyclohexyloxyphenylsulfonyl)diazomethane

[0348] PAG14: bis(4-n-butyloxyphenylsulfonyl)diazomethane

[0349] PAG15: bis(4-n-hexyloxyphenylsulfonyl)diazomethane

[0350] PAG16: bis(4-n-octyloxyphenylsulfonyl)diazomethane

[0351] PAG17: bis(4-n-decyloxyphenylsulfonyl)diazomethane

[0352] PAG18: bis(4-n-dodecyloxyphenylsulfonyl)diazomethane TABLE 6Comparative Example Example 4 5 6 7 8 25 26 27 28 29 30 Polymer A 80 8080 80 80 80 80 80 80 80 80 PAG6 3.00 PAG10 3.22 PAG11 3.44 PAG12 3.41PAG13 4.07 PAG14 3.66 PAG15 4.10 PAG16 4.54 PAG2 4.29 PAG17 4.98 PAG185.42 Basic compound A 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3Surfactant A 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Solvent A 385385 385 385 385 385 385 385 385 385 385

[0353] The amounts of PAG10 to PAG18 and PAG 2 were adjusted so that thenumber of moles of PAG10 to PAG18 and PAG 2 was the same as the numberof moles of PAG6.

[0354] The resist solutions were filtered, then, the same stepsincluding spin coating, baking, KrF excimer laser exposing and PEB wererepeated in the same manner as in Examples 1-24 and Comparative Examples1-3. After developing, the numbers of foreign particles visuallyobserved in 100 square μm were counted by using scanning electronmicroscope (TDSEM available from Hitachi, Ltd. model S9200) whichenables more detailed observation. The results are shown in Table 2.TABLE 7 Comparative Example Example 4 5 6 7 8 25 26 27 28 29 30 Numberof 16-20 16-20 11-15 40-50 100≦ ≦3 ≦3 ≦3 ≦3 ≦3 ≦3 debris afterdevelopment

[0355] There have been described chemical amplification type resistcompositions comprising a specific sulfonyldiazomethane containing along-chain alkylphenyl or long-chain alkoxyphenyl group as the photoacidgenerator. The compositions have many advantages including improvedresolution, improved focus latitude, minimized line width variation orshape degradation even on long-term PED, minimized debris left aftercoating, development and peeling, and improved pattern profile afterdevelopment. Because of high resolution, the compositions are suited formicrofabrication, especially by deep UV lithography.

[0356] Japanese Patent Application No. 2001-300345 is incorporatedherein by reference.

[0357] Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that the invention may bepracticed otherwise than as specifically described without departingfrom the scope of the appended claims.

1. A sulfonyldiazomethane compound having the following general formula(1):

wherein R is independently hydrogen or a substituted or unsubstituted,straight, branched or cyclic alkyl or alkoxy group of 1 to 4 carbonatoms, G is SO₂ or CO, R³ is a substituted or unsubstituted, straight,branched or cyclic alkyl group of 1 to 10 carbon atoms or a substitutedor unsubstituted aryl group of 6 to 14 carbon atoms, p is 1 or 2, q is 0or 1, satisfying p+q=2, n is 0 or 1, m is an integer of 3 to 11, and kis an integer of 0 to
 4. 2. A sulfonyldiazomethane compound having thefollowing general formula (1a):

wherein R is independently hydrogen or a substituted or unsubstituted,straight, branched or cyclic alkyl or alkoxy group of 1 to 4 carbonatoms, n is 0 or 1, m is an integer of 3 to 11, and k is an integer of 0to
 4. 3. A photoacid generator for a chemical amplification type resistcomposition comprising the sulfonyldiazomethane compound of claim 1 or2.
 4. A chemical amplification type resist composition comprising (A) aresin which changes its solubility in an alkaline developer under theaction of an acid, and (B) the sulfonyldiazomethane compound of claim 1which generates an acid upon exposure to radiation.
 5. A chemicalamplification type resist composition comprising (A) a resin whichchanges its solubility in an alkaline developer under the action of anacid, (B) the sulfonyldiazomethane compound of claim 1 which generatesan acid upon exposure to radiation, and (C) a compound capable ofgenerating an acid upon exposure to radiation, other than component (B).6. The resist composition of claim 4 or 5 wherein the resin (A) has suchsubstituent groups having C—O—C linkages that the solubility in analkaline developer changes as a result of scission of the C—O—C linkagesunder the action of an acid.
 7. The resist composition of claim 6wherein the resin (A) is a polymer containing phenolic hydroxyl groupsin which hydrogen atoms of the phenolic hydroxyl groups are substitutedwith acid labile groups of one or more types in a proportion of morethan 0 mol % to 80 mol % on the average of the entire hydrogen atoms ofthe phenolic hydroxyl groups, the polymer having a weight averagemolecular weight of 3,000 to 100,000.
 8. The resist composition of claim7 wherein the resin (A) is a polymer comprising recurring units of thefollowing general formula (2):

wherein R⁴ is hydrogen or methyl, R⁵ is a straight, branched or cyclicalkyl group of 1 to 8 carbon atoms, x is 0 or a positive integer, y is apositive integer, satisfying x+y≦5, R⁶ is an acid labile group, S and Tare positive integers, satisfying 0<T/(S+T)≦0.8, wherein the polymercontains units in which hydrogen atoms of phenolic hydroxyl groups arepartially substituted with acid labile groups of one or more types, aproportion of the acid labile group-bearing units is on the average frommore than 0 mol % to 80 mol % based on the entire polymer, and thepolymer has a weight average molecular weight of 3,000 to 100,000. 9.The resist composition of claim 6 wherein the resin (A) is a polymercomprising recurring units of the following general formula (2a′):

wherein R⁴ is hydrogen or methyl, R⁵ is a straight, branched or cyclicalkyl group of 1 to 8 carbon atoms, R⁶ is an acid labile group, R^(6a)is hydrogen or an acid labile group, at least some of R^(6a) being acidlabile groups, x is 0 or a positive integer, y is a positive integer,satisfying x+y≦5, M and N are positive integers, L is 0 or a positiveinteger, satisfying 0<N/(M+N+L)≦0.5 and 0<(N+L)/(M+N+L)≦0.8, wherein thepolymer contains on the average from more than 0 mol % to 50 mol % ofthose units based on acrylate and methacrylate, and also contains on theaverage from more than 0 mol % to 80 mol % of acid labile group-bearingunits, based on the entire polymer, and the polymer has a weight averagemolecular weight of 3,000 to 100,000.
 10. The resist composition ofclaim 6 wherein the resin (A) is a polymer comprising recurring units ofthe following general formula (2a″):

wherein R⁴ is hydrogen or methyl, R⁵ is a straight, branched or cyclicalkyl group of 1 to 8 carbon atoms, R⁶ is an acid labile group, R^(6a)is hydrogen or an acid labile group, at least some of R^(6a) being acidlabile groups, x is 0 or a positive integer, y is a positive integer,satisfying x+y≦5, yy is 0 or a positive integer, satisfying x+yy≦5, Aand B are positive integers, C, D and E each are 0 or a positiveinteger, satisfying 0<(B+E)/(A+B+C+D+E)≦0.5 and0<(C+D+E)/(A+B+C+D+E)≦0.8, wherein the polymer contains on the averagefrom more than 0 mol % to 50 mol % of those units based on indene and/orsubstituted indene, and also contains on the average from more than 0mol % to 80 mol % of acid labile group-bearing units, based on theentire polymer, and the polymer has a weight average molecular weight of3,000 to 100,000.
 11. The resist composition of any one of claims 6 to10 wherein the acid labile group is selected from the group consistingof groups of the following general formulae (4) to (7), tertiary alkylgroups of 4 to 20 carbon atoms, trialkylsilyl groups whose alkylmoieties each have 1 to 6 carbon atoms, oxoalkyl groups of 4 to 20carbon atoms, and aryl-substituted alkyl groups of 7 to 20 carbon atoms,

wherein R¹⁰ and R¹¹ each are hydrogen or a straight, branched or cyclicalkyl having 1 to 18 carbon atoms, and R¹² is a monovalent hydrocarbongroup of 1 to 18 carbon atoms which may contain a heteroatom, a pair ofR¹⁰ and R¹¹, R¹⁰ and R¹², or R¹¹ and R¹² may together form a ring, withthe proviso that R¹⁰, R¹¹, and R¹² each are a straight or branchedalkylene of 1 to 18 carbon atoms when they form a ring, R¹³ is atertiary alkyl group of 4 to 20 carbon atoms, a trialkysilyl group inwhich each of the alkyls has 1 to 6 carbon atoms, an oxoalkyl group of 4to 20 carbon atoms, or a group of the formula (4), z is an integer of 0to 6, R¹⁴ is a straight, branched or cyclic alkyl group of 1 to 8 carbonatoms or an aryl group of 6 to 20 carbon atoms which may be substituted,h is 0 or 1, i is 0, 1, 2 or 3, satisfying 2h+i=2 or 3, R¹⁵ is astraight, branched or cyclic alkyl group of 1 to 8 carbon atoms or anaryl group of 6 to 20 carbon atoms which may be substituted, R¹⁶ to R²⁵are each independently hydrogen or a monovalent hydrocarbon group of 1to 15 carbon atoms which may contain a heteroatom, R¹⁶ to R²⁵, takentogether, may form a ring, each of R¹⁶ to R²⁵ is a divalent hydrocarbongroup of 1 to 15 carbon atoms which may contain a heteroatom when theyform a ring, or two of R¹⁶ to R²⁵ which are attached to adjoining carbonatoms may bond together directly to form a double bond.
 12. The resistcomposition of claim 4 further comprising (D) a basic compound.
 13. Theresist composition of claim 4 further comprising (E) an organic acidderivative.
 14. The resist composition of claim 4 further comprising anorganic solvent which contains a propylene glycol alkyl ether acetate,an alkyl lactate or a mixture thereof.
 15. A process for forming apattern, comprising the steps of: applying the resist composition of anyone of claims 4 to 14 onto a substrate to form a coating, heat treatingthe coating and exposing the coating to high energy radiation with awavelength of up to 300 nm or electron beam through a photomask,optionally heat treating the exposed coating, and developing the coatingwith a developer.